Designation: D 1493 – 97

Standard Test Method for

Solidification Point of Industrial Organic Chemicals1
This standard is issued under the fixed designation D 1493; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 1015 Test Method for Freezing Points of High Purity

1.1 This test method covers a general procedure for deter- Hydrocarbons3
mining the solidification point of most organic chemicals D 1016 Test Method for Purity of Hydrocarbons from
having appreciable heats of fusion and solidification points Freezing Points3
between −20 and +150°C. D 3437 Practice for Sampling and Handling Liquid Cyclic
1.2 This test method is applicable only to relatively pure Products2
compounds. Values obtained for grossly impure compounds D 3438 Practice for Sampling and Handling Naphthalene,
can be low because of the freezing out of one component Maleic Anhydride, and Phthalic Anhydride2
during the determination. D 3852 Practice for Sampling and Handling Phenol and
1.3 In order that the test method may be used on many Cresyl Acid2
materials, a choice of certain alternatives and a selection of E 1 Specification for ASTM Thermometers4
apparatus are permitted. The report (Section 12) requires that E 29 Practice for Using Significant Digit in Test Data to
the selected alternatives must be stated. Materials to which the Determine Conformance with Specifications5
test method is applicable in particular detail include phenol, E 77 Test Method for Inspection and Verification of Ther-
naphthalene, phthalic anhydride, and maleic anhydride. mometers4
1.4 The following applies to all specified limits in this test 2.2 Other Document:
method: for purposes of determining conformance with this OSHA Regulations, 29 CFR, paragraphs 1910.1000 and
test method, an observed value or a calculated value shall be 1910.12006
rounded off “to the nearest unit” in the right-hand digit used in 3. Terminology
expressing the specification limit, in accordance with the
rounding-off method of Practice E 29. 3.1 Definitions:
3.1.1 solidification point—an empirical constant defined as
NOTE 1—A companion test method is Test Method D 852. the temperature at which the liquid phase of a substance is in
1.5 This standard does not purport to address all of the approximate equilibrium with a relatively small amount of the
safety concerns, if any, associated with its use. It is the same substance in its solid phase.
responsibility of the user of this standard to establish appro- 3.1.1.1 Discussion—Solidification point is distinguished
priate safety and health practices and determine the applica- from freezing point, which is described in Test Method D 1015.
bility of regulatory limitations prior to use. For specific hazard An interpretation of mole percent purity in terms of freezing
statements, see Section 8. point is given in Test Method D 1016.
2. Referenced Documents 4. Summary of Test Method
2.1 ASTM Standards: 4.1 Solidification point is measured by noting the maximum
D 850 Test Method for Distillation of Industrial Aromatic temperature reached during a controlled cooling cycle after the
Hydrocarbons and Related Materials2 appearance of a solid phase in a liquid sample.
D 852 Test Method for Solidification Point of Benzene2
5. Significance and Use
5.1 This test method is suitable for setting specifications on

1
This test method is under the jurisdiction of ASTM Committee D16 on
3
Aromatic Hydrocarbons and Related Chemicals and is the direct responsibility of Annual Book of ASTM Standards, Vol 05.01.
4
Subcommittee D16.04 on Instrumental Analysis. Annual Book of ASTM Standards, Vol 14.03.
5
Current edition approved Feb. 10, 1997. Published September 1997. Originally Annual Book of ASTM Standards, Vol 14.02.
6
published as D 1493 – 57 T. Last previous edition D 1493 – 92. Available from Superintendent of Documents, U.S. Government Printing
2
Annual Book of ASTM Standards, Vol 06.04. Office, Washington, DC 20402.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

1
 D 1493
compounds of the type described in Section 1. It is also suitable
for use as an intense quality-control tool and in development
and research work involving these compounds.
6. Apparatus
6.1 Thermometer—An etched-stem liquid-in-glass ther-
mometer having a range of no more than 30°C shall be used. It
shall be graduated in subdivisions no greater than 0.1°C.
Unless otherwise specified, it shall be calibrated, for 76-mm
immersion, at no fewer than three points. These shall include
the approximate solidification point of the material being tested
and two other points, respectively, about 5°C above and below
the solidification point. A total immersion thermometer can be
used if it is specified for testing a particular material, as, for
example, benzene. (See Test Method D 852.) The thermometer
shall conform to Specification E 1. It should be so chosen that
the graduation at which the solidification point is to be
observed is not hidden from view when the thermometer is
inserted in the sample container. Suitable thermometers are
ASTM Thermometers 89C to 96C, inclusive. Table 1 lists FIG. 1 Stirrer
several of these thermometers and the materials for which,
respectively, they are useful in particular in accordance with 6.5.2 An electric heater that is fully adjustable as described
this test method. A thermometer, for example ASTM Ther- in Test Method D 850, or a bunsen or similar gas burner (see
mometer 17C, 18C, or 91C, is needed when the average Section 9.2), or both.
temperature of the emergent mercury column of the 6.6 Insulation Board—A sheet of hard insulation board 3 to
solidification-point thermometer is measured.

TABLE 1 ASTM Thermometers for Solidification Point

Selected Standardization Average Temperature of Emergent
ASTM Number Range of Temperature, °C Material for Test
Temperature,° C Mercury Column, °C
91C 20 to 50 40 25 phenol
92C 40 to 70 52 25 maleic anhydride
93C 60 to 90 80 30 naphthalene
96C 120 to 150 130 35 phthalic anhydride

6-mm thick and 15 cm square, with a circular hole 50 mm in

6.2 Specimen Container—A standard heat-resistant glass
diameter in the center of it, is needed if the drying procedure
test tube with lip shall be used. The test tube shall measure 25
given in 9.2 is used.
mm in outside diameter and 150 mm in length.
6.3 Stirrer (see Fig. 1)—The stirrer shall consist of a 1-mm NOTE 2—Items described in 6.7, 6.8, and 6.9, are not essential for
diameter (B&S gage 18), corrosion-resistant wire bent into a routinely testing materials that have solidification points substantially
above room temperature, for example above 30°C; but, for referee testing,
series of three circular loops about 25 mm apart at right angles these items shall be used always, regardless of the solidification points of
to the shaft, the circle of each loop being about 20 mm in the materials being tested.
diameter, so that the stirrer can move freely in the annular
space between the inner wall of the specimen container and the 6.7 Air Jacket—A standard heat-resistant glass tube with
thermometer stem when the latter is inserted in the container. lip, 38 mm in outside diameter and 200 mm in length, shall be
The shaft of the stirrer may be of any convenient length not less fitted with a cork stopper bored with a hole of 25 to 26-mm
than 150 mm, and shall pass through an off-center hole in a diameter and into which the specimen container is to be
two-hole cork stopper, the center hole of which holds the inserted up to its lip.
thermometer. The upper end of the shaft may be attached to a 6.8 Cooling Bath—A 2-L beaker or similar suitable con-
reciprocating device for mechanical stirring, or may be formed tainer having an effective depth of at least 175 mm shall be
into a loop to facilitate lifting it for stirring by hand. filled with a cooling medium, which shall be glycerin for
operating at temperatures between 145 and 25°C, water and ice
6.4 Flasks:
between 25 and 0°C, and alcohol and dry ice between 0
6.4.1 A 200-mL, side-tube, heat-resistant glass distillation and −25°C. A thermostatically controlled agitated bath may be
flask as described in Test Method D 850 and used optionally. (See Fig. 2 for assembly of apparatus.)
6.4.2 Two narrow-neck, heat-resistant glass Erlenmeyer 6.9 Clamp and Ring Stand—A clamp, attached to a stand,
flasks, 400-mL capacity each. holds the air jacket rigidly just below its lip when it is
6.5 Heaters: immersed in the cooling bath to a depth between 160 and 200
6.5.1 A hot plate, and mm.

2
 D 1493

FIG. 3 Thermometric Reference Cell

FIG. 2 Apparatus for Determining Solidification Point

NOTE 3—Items listed in 6.10-6.15 inclusive, are required only for

checking the accuracy of the thermometer at the solidification point of the
material being tested. This check is desirable to detect changes that occur
in a thermometer with time and use and to minimize errors generally.7
6.10 Thermometric Cell—A sealed glass cell made from
standard-wall glass tubing, 38 mm in outside diameter, and
about 140 mm in length, has a thermometer well, 120-mm
deep, formed as an integral part lengthwise in it. The cell
contains a relatively pure crystallizable compound of known
freezing point that fills it to a level about 10 mm above the
height of the 76-mm immersion mark of a partial immersion
thermometer when the latter is inserted in the well down to the
bottom. The well shall be made from 10-mm tubing, about 8
mm in inside diameter. (See Fig. 3.) For a total immersion
thermometer, the lengths of the cell and the well shall be
increased to fit. The cell shall have a calibration temperature,
Tc, determined with a platinum resistance thermometer and
assigned to it for use as a thermometric standard. (See Section FIG. 4 Reference Cell in Vacuum Flask
10.)
6.11 Vacuum Flask—An open-mouthed Dewar-type of 6.13 Cradle—Two pieces of fireproof, 6.4-mm board are
vacuum-jacketed flask is needed. Its capacity shall be nomi- needed to support the thermometric cell in the oven. The
nally 500-mL in size. It shall be provided with a base to hold dimensions of each piece shall be about 120 mm in length, 70
it upright. (See Fig. 4.) mm in width, and between 6 and 12 mm in thickness.
6.12 Oven—An electrically heated oven, preferably with 6.14 Safety Items—For personal protection when handling
internal circulation of air, shall be used if the crystallizable fragile cells with contents of a molten compound that is a
compound described in 6.9 is solid at room temperature. The skin-irritant or that has a melting point above 60°C, the
oven must be thermostatically controlled over the temperature operator will need a pair of heat-resistant gloves, a long rubber
range of 60 to 200°C with tolerance of 610°C at any setting in apron, and a transparent visor.
this range. Its chamber must be large enough to hold the items 6.15 Magnifying Glass—For accurately reading the tem-
described in 6.10, 6.11, 6.12 and 6.13 at the same time. A perature indicated by the thermometer, it is advantageous to
chamber of satisfactory size shall be cubic, 500 mm to a side. use a magnifying glass, provided with an eyepiece and a
A thermometer shall be inserted at the top with its bulb about cross-hair, and mounted on a friction-slide that fits over the
125 mm below the ceiling of the chamber. thermometer stem.
7. Reagents and Materials
7
Enagonio, D. P., Pearson, E. G., and Saylor, C. P. Temperature—Its Measure-
ment and Control in Science and Industry, Reinhold Publishing Corp., New York, 7.1 Cork Stoppers—Suitable corks to be used as described
NY, Vol 3, Part 1, 1962, pp. 219–230. in 6.2, 6.3, and 6.4.

3
 D 1493
7.2 Cooling Medium—Technical grade glycerin, technical fresh drying agent on the same sample. After drying the
grade methanol or denatured alcohol, water, ice, and dry ice for sample, proceed as described in 10.1.
use with the cooling bath. 10.4 In an alternative method, when specified, dry the
7.3 Drying Agents—A molecular sieve zeolite with 4A size sample by heating it to its initial boiling point. Support the
of pores shall be used for drying liquid hydrocarbons and distillation flask on the asbestos board over the bunsen burner
phenol. The zeolite may be in the form of a powder or of or the electric heater by means of the ring stand. Attach the
cylindrical granules about 3 mm in diameter. The granules are clamp to the lower part of the neck of the flask. Transfer about
preferred. The pore size is critical, because pores larger than 100 g of the sample to the flask and place a solid cork stopper
4A will absorb some hydrocarbons preferentially. Sodium in the neck. Heat the flask slowly and allow the sample to melt
hydroxide pellets can be used for drying liquid hydrocarbons and then to boil gently. Any water present in the sample will
and other nonacidic compounds. Anhydrous calcium sulfate condense in the neck of the flask. If considerable water is
granules, free of dust, can also be used. present, it will distill out of the side tube of the flask and it
7.4 Packing Materials—Cotton wadding, cloth wipers, and should be collected in a receiver and then discarded. This
glass wool for packing around glass cells of hot, molten method shall not be used for materials that have initial boiling
compounds. Thin aluminum foil, light duty wrap, will also be points below 80°C or above 260°C. Allow the dry condensed
needed as described in 10.10. liquid to rise in the neck of the flask by further heating, for not
more than 1 min, until the liquid just reaches the side tube.
8. Hazards Remove the source of heat and the stopper. Let the sample cool
8.1 Consult current OSHA regulations, supplier’s Material for 1 min. Then warm the neck of the flask above the side tube
Safety Data Sheets, and local regulations for all materials used with a very small flame of the bunsen burner to drive off any
in this test method. condensed moisture. Then stopper the flask with a dry cork. Let
the sample cool until it can be poured conveniently and safely;
9. Sampling and Handling while its temperature is still at least 10°C above its solidifica-
9.1 Sample the material in accordance with Practices tion point, swirl it in the flask to ensure homogeneity, and pour
D 3432, D 3438, and D 3852. enough of it into the specimen container to reach a depth of
about 100 mm. Then proceed as described in 11.1.
10. Preparation of Sample 10.5 If the sample is not to be fired but is to be tested as
10.1 If a sample is a solid mass at room temperature, melt received, pour it in liquid form into the specimen container to
the entire sample by heating it at about 10°C above its a depth of about 100 mm. If it is not liquid at room
solidification point and swirl it for homogeneity before pouring temperature, heat about 100 g of it in a 400-mL Erlenmeyer
the portion, as specified below, for drying and analysis, or both. flask to a temperature about 10°C above its melting point and
10.2 If the sample is to be dried before being tested, place swirl it for homogeneity before pouring it into the specimen
about 100 g of the material in a 400-mL Erlenmeyer flask and container. Use this procedure in the testing of refined naphtha-
add about 50 g of drying agent, for example, anhydrous lene. Then proceed as described in 11.1.
calcium sulfate or sodium hydroxide pellets. Liquids shall be 10.6 If the sample is a water-immiscible substance, for
dried at room temperature and solids on a hot plate at about example a liquid hydrocarbon, and is specified to be tested
10°C above their solidification point. If the sample is hygro- after saturation with water, proceed as described in 10.6 to
scopic, place a very loosely fitting stopper in the flask. After 15 introduce the sample into the sample container. Then add one
min, decant the sample to another flask and repeat the drying drop, about 0.06 g, of water; stopper the specimen container,
step with occasional stirring. Pour sufficient sample into the and shake it vigorously. Then proceed as described in 11.1.
sample container to fill it to a depth of approximately 100 mm.
Then proceed as described in 10.1. 11. Procedure
10.3 Highly hygroscopic materials, or materials like refined 11.1 The cooling bath temperature shall be 5 to 10°C below
phenol of which the solidification point is very sensitive to the expected solidification point. When the solidification point
moisture, shall be dried as follows: Add 15 g of 4A molecular of the material under test is sensitive to cooling conditions, it
sieve to 100 g of the molten material in a 400-mL Erlenmeyer is desirable to keep the bath at the 5°C differential. Refined
flask; stopper the flask very loosely and place it on a hot plate naphthalene and phenol are two such materials. For naphtha-
at a temperature at least 10°C above the solidification point of lene the cooling bath shall be held at 70 to 75°C, and for phenol
the sample, but not hot enough to cause the sample to boil or at 30 to 35°C, the higher temperature being preferable in each
to decompose. For example, a sample of phenol shall be heated range. Fit the sample container up to its lip into the cork
at 60°C. Heat the sample for 20 min with agitation by swirling stopper of the air-jacket. Fit the thermometer and the stirrer
at 5-min intervals. This method of drying is satisfactory for into the two-hole stopper of the specimen container. Adjust the
phenol containing as much as 2 % water. Quickly transfer the partial-immersion thermometer so that it is immersed up to its
dried sample, including any entrained drying agent, to the 76-mm calibration mark in the specimen. The bottom of the
specimen container to a depth of about 100 mm. The layer of thermometer bulb will then be about 24 mm above the bottom
entrained drying agent, after it has settled in the specimen of the specimen container. Use this procedure exactly when
container, must not exceed a depth of 15 mm. If there is any naphthalene, phenol, phthalic anhydride, or maleic anhydride
doubt as to the completeness of drying, decant the molten is being tested.
sample from the drying agent and repeat the procedure with 11.2 Clamp the assembly, described in 10.1 and illustrated

4
 D 1493
in Fig. 2, to the ring stand and place it so that the air jacket is solidification point of the material in the cell shall be certified
immersed vertically in the cooling bath to a depth at which at by a referee from the measurement made with an accurate
least 100 mm of length of the specimen container is below the platinum-resistant thermometer in the well of the cell. Repeat
surface of the cooling medium. the measurement under comparable conditions with the ther-
11.3 Allow the specimen to cool while stirring it at the rate mometer of unknown accuracy. The difference between the two
of about 60 strokes per minute. A mechanical reciprocating measurements is a correction for the test thermometer at the
device that will simulate hand stirring is permissible. The temperature of the solidification point of the test sample. (See
stirrer should not touch the thermometer or the wall of the 12.4-12.8.)
sample container. Discontinue stirring after an appreciable 11.7 Inspect the thermometer very closely, preferably with a
amount of crystals has formed but while the specimen is still magnifying glass, to make sure that there are no minute cracks
mainly liquid. in the bulb and no air bubbles in the thread or column of
11.4 Observe and record the thermometer readings at regu- mercury. If air bubbles are noted, remove them by cooling the
lar intervals, estimating degrees to the nearest 0.01°C until the thermometer in dry ice and tapping it gently. Place the
temperature rises from minimum, due to supercooling, to a thermometer down to its immersion mark in the cooling bath at
maximum and finally begins to drop. The true maximum the temperature at which the bath will be held for determining
temperature is the solidification point. As the temperature the solidification point of a sample of the compound in the
approaches this point on the rise, thermometer readings should thermometric cell, and hold the thermometer there for at least
be taken at 10-s intervals in order to make sure that the 1⁄2 h. For example, Thermometer 96C shall be conditioned thus

temperature has reached its maximum, and at least three more at about 126°C for use in testing phthalic anhydride.
readings should therefore then be taken at the maximum level, 11.8 If the compound in the thermometric cell is solid, it
until the first drop in temperature is noted. This will ensure must be melted in the oven under controlled conditions at a
against mistaking a temporary plateau of temperature level for temperature above its melting point by 40 to 60°C. An
the true maximum temperature. If there is any doubt about the increment of 60°C is preferred. For example, phthalic anhy-
trend of the readings, plotting a graph of temperature versus dride is melted at 190°C, oven temperature. First, prepare a
time on linear graph paper will help in interpreting the data cradle to hold the cell, by placing the two pieces of fireproof
clearly. Note the experimental maximum temperature, te. (See board about 20 mm apart on the oven shelf, laying them flat
Section 12 for temperature corrections to be added to te.) with their long sides parallel. Place the thermometric cell lying
NOTE 4—The accuracy of the thermometer readings can be increased down lengthwise in the groove thus formed by the boards and
by using a magnifying glass that assures a reading on a line of sight with the nipple, where the glass was sealed in the manufacture
perpendicular to the stem of the thermometer. This should be done in the of the cell, facing upward. Place the vacuum flask on the oven
testing of refined naphthalene and phthalic anhydride. Also, for the record, floor at the same time for conditioning. If the vacuum flask is
the average temperature, t0, of the emergent mercury column should be
taken. (See 11.1-11.4.)
one that is set in its base with uintaite cement, do not heat it
NOTE 5—If the temperature rise after initial crystallization exceeds
above 120°C. If the compound in the thermometric cell is
0.5°C, remelt the specimen by warming it gently in the specimen container normally liquid or if its solidification point is below 45°C, the
and repeat the test. Seed with two or three small crystals of the sample conditioning of the cell and the vacuum flask shall be carried
when the temperature is 0.2 to 0.3°C below the expected solidification out at an appropriate temperature in the cooling bath instead of
point. When the sample is a liquid, these crystals may be obtained by the oven, in a way similar to that used for the thermometer
freezing a small quantity of the liquid in a test tube immersed directly in described in 11.7. For example, a cell containing benzene shall
the cooling bath. Some compounds have more than one solidification
point due to the occurrence of metastable phases. Therefore it is essential
be conditioned in cold water at 4.5 to 5.0°C, and a cell
to select, for the seeding, crystals known to be of the desired stable phase containing phenol shall be conditioned in hot water at 70 to
as found by a previous determination of solidification point. As an 80°C. An alternative way to condition the vacuum flask is to
alternative to induce crystallization, a chilled wire may be substituted in store within it, for 1⁄2h, a thermometric cell, for example a
place of small crystals of the sample. duplicate or a dummy, which itself has been conditioned at the
NOTE 6—The procedure described in 10.5 to 10.10 inclusive, is appropriate temperature.
required only for checking the accuracy of the thermometer at the
11.9 Close the oven door and leave it closed for 10 min.
solidification point of the material being tested.
Then open the door and rotate the cell one complete turn in the
11.5 When the accuracy of the thermometer is to be groove of the cradle before reclosing the door. Repeat this
checked, as indicated in Note 3 and Note 6, make the check by turning every 2 min until the crystals in the cell have melted
means of a thermometric cell. Check immediately before completely. For phthalic anhydride, repeat this turning four or
determining the solidification point of the sample. To make five times; the crystals will be completely molten in about 20
sure that the temperature of the emergent mercury column in min. This melting procedure is fairly critical in order to avoid
the stem of the thermometer is the same during the check as breakage of cells containing crystals that melt at about 80°C or
during the determination of solidification point, carry out both higher and that are fused together in a lump in the cell. Using
operations at the same spot. heat-insulating gloves, take the vacuum flask out and set it on
11.6 The thermometric cell contains a crystallizable com- its stand. Then wrap the hot cell in cotton wadding or in several
pound. This shall be preferably a pure sample of the same layers of cloth wipers, with both ends of the cell exposed. With
compound as the sample of which the solidification point is to due precaution against burns, grasp the bundled cell and shake
be determined with the thermometer that is being checked. The it vigorously, end to end in the direction of its long axis, until

5
 D 1493
a slurry or mush of fine crystals appears in it. This fairly dense 12.2 In a total immersion thermometer, the emergent stem
mush should appear practically all at once. Its occurrence can correction is calculated differently and is needed only when the
be promoted by directing a gentle jet of air at the top of the cell thermometer is used at partial immersion. This correction
or by touching the top with a lump of dry ice. Then continue compensates for the difference, (tb − to), between tb, the tem-
the shaking for 5.0 s longer and, with a layer of cloth wipers or perature of the bulk of the thermometer, and to, the observed
cotton wadding about the cell to provide a snug fit in the average temperature of the emergent column of mercury. One
vacuum flask, insert the cell right side up in the conditioned way to assign a numerical value to tb is to measure te with a
vacuum flask; lay additional wadding or glass wool over it, as thermometer of which the scale is certified to be accurate
shown in Fig. 4, sufficiently loose to allow the thermometer within 0.02°C and to take tb = te. Another way is to repeat the
later to be inserted in the well of the cell. procedure without using the air jacket; then, after observing te,
11.10 Insert the thermometer, which has been conditioned in let the specimen remain in the apparatus for 20 min more,
accordance with 10.7, into the well of the cell. The fit must be measure to again, and take the temperature of the cooling bath
snug, to ensure good heat transfer through the wall of the well for the value of tb in the term (tb − ts).
to the bulb of the thermometer. If the fit is loose, either wrap a 12.3 The emergent stem correction is algebraically additive.
turn of aluminum foil around the bulb only, or pour into the Its value for a mercury-in-glass thermometer graduated in
well about 0.5 mL of glycerin preheated to just slightly below degrees Celsius is calculated by the formula 0.00016 N
the solidification point of the material in the cell, in order to (tb − to), where N is the number of degrees emergent from the
improve heat transfer. Adjust the top wadding about the stem of bath.
the thermometer so as not to obscure the mercury thread from 12.4 Report the corrected temperature as follows:
sight. After 5 min read the temperature to the nearest 0.01°C, tn 5 ts 1 0.00016 n ~ts 2 to! for a partial immersion thermometer
using a magnifying glass to aid in visual estimation of (1)
hundredths of a degree. Read the temperature at regular,
frequent intervals and note its maximum value, the uncorrected or
temperature, Tu. The time to attain the maximum, and then to
reveal a distinct drop in temperature, varies for different t8n 5 ts 1 0.00016 N ~tb 2 to! for a total immersion thermometer
(2)
materials. It must be not less than 10 min. The intervals at
which temperature readings are taken shall be every 2 min after
the first reading until the sixth reading; if the maximum reading If the thermometer scale was certified to be accurate within
is not attained after 15 min total elapsed time, readings shall 0.02°C when the test was made, report tn or t8n as the
then be made at 5-min intervals. After the first 15 min, take the solidification point.
average temperature, To, of the emergent stem of the thermom- 12.5 For referee tests, either the thermometer shall be
eter with another thermometer placed alongside with its bulb at stipulated to be accurate within 0.02°C of scale at the level of
a level about half way along the length of the emergent ts, or the thermometer shall be checked for accuracy, immedi-
mercury column. Do not hold the thermometer that is being ately prior to the measurement of ts. (See Section 10.6 and
checked, because the warmth of one’s fingers can affect the 10.10.) In this check the apparent scalar error is measured. It is
value Tu as much as 0.03°C. the difference, (Te − Tu), between Te, the certified calibration
11.11 Platinum resistance or quartz thermometers may be temperature assigned to the thermometric cell, and Tu, the
used to calibrate the liquid in glass thermometers used in this uncorrected temperature observed with the test thermometer at
test method. the solidification point of the reference compound in the cell. If
this difference is a number between +0.02 and −0.02°C, it shall
12. Temperature Corrections be disregarded as being indistinguishable from zero by this
12.1 If a thermometer other than one of those listed in Table measurement. If the difference is either a positive or a negative
1 was used in this test method, calculate and report a number outside of the range from +0.02 to −0.02°C, inclusive,
temperature correction to be added to te. This correction is it shall be applied as an algebraically additive scalar correction.
called the emergent stem correction. In a partial immersion 12.6 If the thermometer was selected in accordance with
thermometer, this correction compensates for the difference, Table 1 and used in accordance with 10.10, and in general
(ts − to), between ts, the stem temperature at which the scale of whenever the emergent stem temperature is the same in the
the thermometer was standardized, and to, the observed aver- checking procedure for accuracy as in the testing procedure for
age temperature of the emergent column of mercury. (See Test solidification point, that is, whenever T0 = to, report solidifica-
Method E 77.) See Note 6 for reference to to. For ts, see the tion point as follows:
Selected Standardization Temperature in Table 1 or see Table 2 tp 5 ts 1 Kn~ts 2 to! 1 ~Tc 2 Tu! 5 tn 1 ~Tc 2 Tu! (3)
of Specification E 1. The correction is algebraically additive.
Its value is calculated by the formula Kn(ts − to), where K is the
12.7 If a partial immersion thermometer other than one
differential coefficient of expansion between the liquid in the
listed in Table 1 is used, and whenever To = to, report solidi-
thermometer and the glass of which the thermometer is made.
fication point as follows:
For mercury-in-glass thermometers graduated in degrees Cel-
sius, K = 0.00016; and n is the number of degrees Celsius tq 5 tm 1 ~Tc 2 Tu! 2 Km~Te 2 To! (4)
between the start of the scale on a partial immersion thermom-
eter and te, the experimental maximum temperature. where m is the number of degrees on the scale between Tu

6
 D 1493
and the start of the scale. confirm that the following requirements have been met:
12.8 If a total immersion thermometer is used, report 13.4.1 The sample was tested as received,
solidification point as follows: 13.4.2 The air jacket and cooling bath were used,
t8q t8n 1 ~Tc 2 Tu! 2 KM~Tc 2 Tc! (5) 13.4.3 The temperature of the cooling bath was between
121 and 126°C, and
where M is the number of degrees on the scale between Tu 13.4.4 ASTM Thermometer 96C was used. The report shall
and the level of the surface of the molten reference compound also include the following:
in the cell. 13.4.5 The value of te,
13.4.6 That scale error was stipulated to be negligible if it is
13. Report neglected, and
13.1 For completeness of record and for referee tests, report 13.4.7 The value of tp, if, under 13.4.6, the report does not
the following information: state that scale error was stipulated to be negligible.
13.1.1 Whether the sample was tested dry or water-saturated 13.5 When the sample is tested water-saturated and a
or as received, standard correction for the effect of the moisture is specified, as
13.1.2 Which method of drying, if any, was used, for benzene as described in Test Method D 852, add the
13.1.3 Which drying agent, if any, was used, correction and report the corrected solidification point.
13.1.4 Whether the air-jacket and cooling bath were used,
13.1.5 Temperature of the cooling-bath, if it was used, 14. Precision and Bias
13.1.6 ASTM thermometer that was used,
14.1 For the materials reported respectively in accordance
13.1.7 te, the experimental maximum temperature, as the
with 13.2, 13.3, and 13.4, the precision of the solidification
average of at least three readings of the maximum value, to the
point at the level of 95 % confidence is as follows:
nearest 0.01°C (see 10.4), and
Refined Material Repeatability, °C Reproducibility, °C
13.1.8 If one of the thermometers listed in Table 1 was used Phenol 0.03 0.07
and if its scale was stipulated to be accurate within 0.02°C Naphthalene 0.05 0.10
when the test was made, report te as the solidification point. Phthalic anhydride 0.05 0.11

NOTE 7—See Section 11 for calculations to be made if a thermometer 14.2 For a measure of precision in the checking procedure
other than one of those listed in Table 1 was used or if a temperature described in 10.10, the standard deviation of Tu has been found
correction must be added to te. to be no greater than 0.005°C in repeatability. Tu is the
13.2 For referee tests of refined phenol, the report shall uncorrected temperature observed with a partial immersion
confirm that the following requirements have been met: thermometer at the solidification point of the reference com-
13.2.1 The sample was tested dry, pound in a thermometric cell.
13.2.2 The drying method described in 13.1 was used, 14.3 For a measure of the accuracy that is attainable in the
13.2.3 The drying agent used was molecular sieve 4A in checking procedure described in 10.10, the difference
granular form, (Tc − T8u) has been taken. Tc is the certified temperature
13.2.4 The air jacket and cooling bath were used, assigned to a thermometric cell for the solidification point of
13.2.5 The temperature of the cooling bath was between 30 the reference compound in it. T8u is a special value of Tu: in the
and 35°C, and special case in which Tu is observed with an accurate ther-
13.2.6 ASTM Thermometer 91C was used. The report shall mometer requiring no scalar correction, Tu = T8u. The follow-
also include the following: ing limits have been found for the value of (Tc − T8u):
13.2.7 The value of te, Numerical Limits of the
Value of (Tc − T8u)
13.2.8 That scale error was stipulated to be negligible if it is Reference Compound in Minimum Value, Maximum Value,
neglected, and Thermometric Cell deg°C deg°C
13.2.9 The value of tp, if, under 13.2.8, the report does not Phenol −0.012 −0.022
Naphthalene +0.020 −0.031
state that scale error was stipulated to be negligible. Phthalic anhydride −0.095 −0.112
13.3 For referee tests of refined naphthalene, the report shall
conform that the following requirements have been met: 14.4 The following criteria should be used for judging the
13.3.1 The sample was tested as received, acceptability of results for maleic anhydride:
13.3.2 The air jacket and cooling bath were used, 14.4.1 Intermediate Precision (formerly called
13.3.3 The temperature of the cooling bath was between 70 Repeatability)—The standard deviation of results (each the
and 75°C, and average of duplicates), obtained by the same analyst on
13.3.4 ASTM Thermometer 93C was used. The report shall different days, has been estimated to be 0.012°C at 10 dP. Two
also include the following: such values should be considered suspect (95 % confidence
13.3.5 The value of te, level) if they differ by more than 0.05°C.
13.3.6 That scale error was stipulated to be negligible if it is 14.4.2 Reproducibility (Multilaboratory)—The standard de-
neglected, and viation of results (each the average of duplicates), obtained by
13.3.7 The value of tp, if, under 13.3.6, the report does not analysis in different laboratories, has been estimated to be
state that scale error was stipulated to be negligible. 0.077°C at 9 dP. Two such values should be considered suspect
13.4 For referee tests of phthalic anhydride, the report shall (95 % confidence level) if they differ by more than 0.25°C.

7
 D 1493
15. Keywords
15.1 heat of fusion; heat of solidification; solidification
point

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