Designation: E1782 – 08

Standard Test Method for

Determining Vapor Pressure by Thermal Analysis1
This standard is issued under the fixed designation E1782; 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 E1142 Terminology Relating to Thermophysical Properties

1.1 This test method describes a procedure for the determi- E2071 Practice for Calculating Heat of Vaporization or
nation of the vapor pressure of pure liquids or melts from Sublimation from Vapor Pressure Data
boiling point measurements made using differential thermal SI 10 Standard for Use of the International System of Units
analysis (DTA) or differential scanning calorimetry (DSC) (SI) The Modern Metric System
instrumentation operated at different applied pressures. 3. Terminology
1.2 This test method may be used for the temperature range
273 to 773 K (0 to 500 °C) and for pressures between 5 kPa to 3.1 Definitions:
2 MPa. These ranges may differ depending upon the instru- 3.1.1 The following terms are applicable to this test method
mentation used and the thermal stability of materials tested. and can be found in either Terminology E473 or Terminology
Because a range of applied pressures is required by this test E1142: boiling pressure, boiling temperature, differential scan-
method, the analyst is best served by use of instrumentation ning calorimetry (DSC), differential thermal analysis (DTA),
referred to as high pressure differential thermal instrumentation vapor pressure, vaporization point, vaporization temperature.
(HPDSC or HPDTA). 3.2 Symbols:
1.3 The values stated in SI units are to be regarded as 3.2.1 A, B, C—Antoine vapor pressure equation (1)3 con-
standard. No other units of measurement are included in this stants (log10, kPa, K):
standard. Antoine vapor pressure equation: Log10 P 5 A 2B/~T 1 C!
1.4 There is no ISO standard equivalent to this test method.
1.5 This standard does not purport to address all of the where:
safety concerns, if any, associated with its use. It is the P = vapor pressure, kPa, and
T = temperature, K.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 4. Summary of Test Method
bility of regulatory limitations prior to use.
4.1 A specimen in an appropriate container is heated at a
2. Referenced Documents constant rate within a DTA or DSC instrument operated under
an applied constant vacuum/pressure between 5 kPa and 2 MPa
2.1 ASTM Standards:2
until a boiling endotherm is recorded. Boiling is observed at
E177 Practice for Use of the Terms Precision and Bias in
the temperature where the specimen partial pressure equals the
ASTM Test Methods
pressure applied to the test chamber. The pressure is recorded
E473 Terminology Relating to Thermal Analysis and Rhe-
during observance of the boiling endotherm and the boiling
ology
temperature is recorded as the extrapolated onset temperature.
E691 Practice for Conducting an Interlaboratory Study to
This measurement is repeated using new specimens for each of
Determine the Precision of a Test Method
five or more different pressures covering the pressure range of
E967 Test Method for Temperature Calibration of Differen-
interest. The pressure-temperature data are fitted as Log10 P
tial Scanning Calorimeters and Differential Thermal Ana-
and 1/T (K−1) to the Antoine vapor pressure equation (see Fig.
lyzers
1). Vapor pressure values required for specific reports are then
computed from the derived equation.
1
This test method is under the jurisdiction of ASTM Committee E37 on Thermal 4.2 The capability of the assembled system after calibration
Measurements and is the direct responsibility of Subcommittee E37.01 on Calo- should be periodically checked by using this method on pure
rimetry and Mass Loss. water as a reference substance and comparing the derived
Current edition approved March 1, 2008. Published June 2008. Originally
approved in 1996. Last previous edition approved in 2003 as E1782 – 03. DOI: vapor pressure data with the NBS/NRC steam tables attached
10.1520/E1782-08. as Appendix X1.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on The boldface numbers given in parentheses refer to a list of references at the
the ASTM website. end of the text.

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 E1782 – 08
inert gas for elevated pressures or for back-filling after evacu-
ation of the sample chamber is recommended to minimize the
risk of oxidation.
6.3 Partial blockage of the pinhole in the DSC containers
could occasionally be encountered. This may be observed as
noise spikes on the boiling endotherm and shall not be
considered a valid pressure-temperature datum point.

7. Apparatus
7.1 The essential equipment required to provide the mini-
mum instrument capability of this test method includes (see
Fig. 2):
7.1.1 Differential Scanning Calorimeter (DSC) or Differen-
tial Thermal Analyzer (DTA), consisting of:
7.1.1.1 DSC/DTA Test Chamber, composed of a furnace(s)
to provide uniform controlled heating of a specimen and
reference at a constant rate within the 273 to 773 K temperature
range of this test method; a temperature sensor to provide an
indication of the specimen/furnace temperature to 61 K; a
differential sensor to detect a difference (temperature or heat
flow) between the specimen and reference equivalent to 5 mW;
and a means of sustaining an inert gas or vacuum test chamber
environment at pressures above and below ambient.
7.1.1.2 Temperature Controller, capable of executing a
specific temperature program by operating the furnace(s)

FIG. 1 Vapor Pressure Curve with Experimental Data and

Antoine Equation Fit

5. Significance and Use

5.1 Vapor pressure is a fundamental thermophysical prop-
erty of a liquid. Vapor pressure data are useful in process
design and control, in establishing environmental regulations
for safe handling and transport, for estimation of volatile
organic content (VOC), and in deriving hazard assessments.
Vapor pressure and boiling temperature data are required for
Material Safety Data Sheets (MSDS). The enthalpy of vapor-
ization may also be estimated from the slope of the vapor
pressure curve (see Practice E2071).

6. Interferences
6.1 This test method is limited to materials that exhibit a
singular sharp boiling endotherm under the conditions outlined
in this test method.
6.2 Oxidation, pyrolysis, or polymerization of condensed
organic materials retained at temperatures above their ambient
boiling point may be encountered at the elevated pressures of N OTE —“A”, DSC/DTA instrument; “B,” pressure transducer;
this method. This will be observed as an exotherm or a “C,”pressure/vacuum source; “D,” pressure stabilizer; “E,” pressure
significantly broadened endotherm, or both, and shall not be regulator; and “F,” relief valve.
considered a valid pressure-temperature datum point. Use of an FIG. 2 Schematic of Apparatus

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 E1782 – 08
between selected temperature limits to 61 K at a rate of 7.2.2 A balance to weigh specimens or specimen containers,
temperature change of 5 K/min constant within 61 %. or both, to 60.1 mg.
7.1.1.3 Recording Device, to provide a means of acquiring, 7.2.3 A syringe or micropipet to deliver liquid specimens of
storing and displaying measured or calculated signals or both. 1 to 5 µL 610 %.
The minimum output signals are heat flow, temperature and 7.2.4 Pressure relief valve to prevent accidental overpres-
time. surization in the pressure system. A rating of 10 % in excess of
7.1.2 Pressure/Vacuum System, consisting of: the upper use pressure is suggested provided it does not exceed
7.1.2.1 A pressure vessel, or similar means of sealing the the maximum working pressure rating of any individual
test chamber at any applied absolute pressure within the 5 kPa component in the system.
to 2 MPa range of this test method.
7.1.2.2 Source of Pressurized Gas, or vacuum capable of 8. Precautions
sustaining a regulated inert gas pressure to the test chamber of 8.1 Safety Precautions:
between 5 kPa and 2 MPa. 8.1.1 Pressures in addition to ambient are employed in this
7.1.2.3 Pressure Transducer(s), to measure the pressure in test method. Ensure that the pressure/vacuum system is certi-
the test chamber to within 1 % including any temperature fied for operation at the extremes of pressure encountered with
dependence of the transducer(s) over the range of 5 kPa to 2 this test method. Incorporation of a pressure relief device is
MPa. recommended.
NOTE 1—Distance (or dead volume) between the pressure transducer 8.1.2 Adequate provisions shall be available for retention
and the specimen in the test chamber should be minimized to ensure and disposal of any spilled mercury if mercury-containing
accurate recording of the pressure at the time of boiling. pressure devices are employed.
7.1.2.4 Pressure Regulator, or similar device to adjust the
9. Sampling
applied pressure in the test chamber to 62 % of the desired
value. 9.1 Typical specimen sizes used for individual pressure
7.1.2.5 Ballast, or similar means to maintain the applied measurements are 1 to 5 mg of solid or 1 to 5 µL of liquid.
pressure in the test chamber constant to 61 %. Similar size specimens should be used for each individual
7.1.2.6 Valves, to control delivery of the inert gas/vacuum to measurement of a given sample.
the test chamber or to isolate components of the pressure/ 9.2 Samples are assumed to be tested as received. Report
vacuum system, or both. Valves shall be rated in excess of the any special sampling or pretreatment used with this test
2 MPa upper pressure limit of this test method. method.
7.1.3 Containers, (pans, capillary tubes, etc.) that are inert
to the specimen and reference materials and which are of 10. Calibration
suitable structural shape and integrity to contain the specimen 10.1 Perform calibration according to Practice E967, using
and reference in accordance with the following specific re- the heating rate and specimen containers intended for this test
quirements: method. Accomplish temperature calibration at ambient pres-
7.1.3.1 It is imperative that the containers used in this test sure.
method be capable of retaining the specimen in a manner that NOTE 3—The effect of pressure on the melting temperature of pure
minimizes sample loss through vaporization prior to boiling materials used to calibrate the temperature axis has been shown to be
and that promotes the development of vapor-liquid equilibrium <0.01 K at the maximum pressure of this method (4). The effects of
at boiling. When both conditions are met a sharp endotherm vacuum on the heat transfer characteristics and subsequent thermal lag of
with little or no baseline curvature at the onset will be various differential thermal instruments (DSC and DTA) have not been
observed. established. From general experiences these effects should not alter the
temperature axis calibration by more than 1 K at the minimum pressure of
NOTE 2—Studies by ASTM task group E37.01.05 and others (2, 3) have this test method.
determined glass cylindrical containers of 2 to 4 mm inside diameter by 25
10.2 Calibrate the pressure transducer according to the
mm long are suitable for thermocouple inserted style DTA instruments;
and a hermetic sealable pan (approximately 40 µL vol) with a single recommendations of the manufacturer or similar appropriate
pinhole in the center of the lid of #125 µm diameter is suitable for DSC procedure.
instruments. For purposes of this test method, pinhole diameters of 50 to
75 µm are recommended. These pinhole dimensions for DSC containers 11. Procedure
were established specifically for use with heating rates of nominally 5 11.1 Place the specimen and inert reference in suitable
K/min. Use of heating rates other than 5 K/min are not recommended for
containers (see 7.1.3) into the test chamber.
this test method. Higher rates may result in some self-pressurization of the
specimen and lesser rates will extend measurement times and will tend to NOTE 4—If hermetic sealable DSC pans with pinholed lids are used,
promote preboiling vaporization. make sure there is no sample material on the outer surfaces of the
7.2 Auxiliary equipment considered useful in conducting container and that a good hermetic seal is accomplished. Either will result
in preboiling vaporization that at least partially negates the function of the
this test method include: pinhole. Be certain, also, that the pinhole is free of dirt or debris.
7.2.1 A coolant system that can be coupled directly with the
controller to the furnace to hasten its recovery from elevated 11.2 Seal the test chamber and apply the desired pressure.
temperatures or to sustain a subambient temperature to within NOTE 5—It is recommended to flush residual oxygen from the test
61 K of a lower limit temperature. chamber by either purging for several minutes with inert gas or by

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 E1782 – 08
evacuation and back-filling with inert gas. NOTE 9—Deviations from linearity (curvature) due to expected de-
creases in enthalpy of vaporization with temperature (Antoine equation
11.3 Allow the pressure to stabilize and equilibrate the test
“C” constant negative) should not be confused with the abrupt deviation
chamber at a start temperature which shall be at least 30 K due to decomposition or polymerization. Curvature of normal data is
below the expected boiling temperature to ensure stable barely perceptible.
temperature control and baseline.
12.3 Calculate the Antoine vapor pressure equation con-
11.4 Heat the specimen and reference at a constant rate of 5
stants: A, B, and C retaining all available decimals using a
K/min, recording the DSC/DTA curve until the vaporization is
nonlinear least-squares regression program to fit the Antoine
complete.
equation, Log10 P = A − B/(T + C) to the corrected pressure-
11.5 Record the absolute pressure in the test chamber at the
temperature data points. Data for which any of the fitted
time the boiling endotherm is observed.
Antoine equation constants fall outside of ranges given in Note
NOTE 6—Most pressure gauges report pressure relative to ambient 10 shall be rejected.
pressure. In such cases, the measured pressure shall be added to or
subtracted from atmospheric pressure measured by a barometer to obtain NOTE 10—This test method uses the SI units of Kelvin for temperature
absolute pressure. instead of the traditional use of Celsius. The only effect of this change is
to make the “C” constant of the Antoine equation a negative value.
11.6 Restore the test chamber to ambient conditions upon Antoine equation constants (for log10, kPa, and K units) typically fall in
completion of the heating curve. these ranges:4 A, 4.9 to 7.8; B, 750 to 3000; and C, −235 to −3. If a
11.7 Repeat 11.1-11.6 with a new specimen at each of four nonlinear least-squares regression program is not available, a multilinear
or more additional pressures throughout the pressure range least-squares regression program may be used for Antoine equation fitting
capability of the equipment. by making these variable transformations:5 a = A; b = A * C − B; and
c = −C. The fitting equation, now linear in the parameters, is:
NOTE 7—A minimum of five measurements at different pressures are t*log10P5a*t 1 b 1 c*log10P
required for this test method. Additional measurements should improve
the fit of the Antoine vapor pressure equation and reduce the uncertainty 12.4 Using the Antoine equation with constants determined
of the Antoine constants used to calculate the vapor pressure curve. in 12.3, compute a table of pressure-temperature data pairs
encompassing the range of conditions tested including the
12. Calculation boiling point temperatures for pressures of 1000, 101.32 (760
12.1 Determine and tabulate each boiling temperature (as To torr), and 10 kPa and the vapor pressure at 293.15 K (20 °C).
or Te in Fig. 3) along with its corresponding observed pressure,
P. 13. Report
NOTE 8—Traditionally, the extrapolated onset temperature (To) of an 13.1 Report the following information:
endotherm recorded by DSC is used as the transition temperature; the peak 13.1.1 Sample identity, purity (if known or determined, as
maximum temperature (Te) is used for thermocouple inserted DTA well as how it was determined), and source,
configurations. The convention employed during temperature calibration 13.1.2 A table of the corrected pressure-temperature data
shall be used for these calculations. points,
12.2 If necessary, correct the observed pressures and tem- 13.1.3 The Antoine vapor pressure equation constants A, B,
peratures by the amount determined from the calibrations. Plot and C rounded to the nearest 0.000001,
the logarithms of pressure (log10P) versus the reciprocal of the 13.1.4 A table of the computed pressure-temperature data
absolute temperature (1/T, K−1). Examine this plot for any including the boiling point temperatures at 1000, 101.32 (760
abrupt deviation from linearity as evidence of instability. torr), and 10 kPa rounded to the nearest 0.1 K, and the vapor
pressure at 293.15 K (20 °C) rounded to the nearest 0.1 kPa.
13.1.5 A graphic presentation of the vapor pressure curve
including the regression fit to the Antoine vapor pressure
equation, and
13.1.6 Any abrupt deviation from linearity in the vapor
pressure curve and the temperature of its occurrence.
13.1.7 The specific dated version of this test method used.
14. Precision and Bias
14.1 Interlaboratory Study (ILS)—An interlaboratory study
for measurement of vapor pressure by this test method was
conducted in 1995. Two materials were studied: n-heptane and
distilled water. Each of six laboratories measured vapor pres-
sure data for n-heptane; each of six laboratories measured
vapor pressure data for distilled water. Practice E691 was
followed for the ILS design and for the analysis of the data.

4
These ranges were determined by examination of Antoine equation literature
FIG. 3 Boiling Endotherm from DSC/DTA Instrumentation with: and databanks, for example, see Refs (1) and (5).
5
extrapolated Onset, To and Peak Maximum, Te This procedure was described in Ref (6).

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 E1782 – 08
14.2 Test Results—The precision information given below Boiling point (K) 320.4 4.9 5.1 319.0
is for duplicate determinations of vapor pressure data calcu- at 10.0 kPa
Vapor pressure (kPa) 2.1 1.2 1.2 2.3
lated from the derived Antoine equations as described in 12.3. at 93.15 K
14.3 Precision—The terms repeatability and reproducibility
given below are used as specified in Practice E177. Standard
deviations among study results may be calculated by dividing 14.4 Bias:
the third and fourth table columns by 2.8. 14.4.1 Bias for n-Heptane—The values listed in the NIST
14.3.1 Precision for n-Heptane: column in 14.3.1 can be used as accepted reference values as
ILS Repeat- Repro- NIST defined in Practice E177. The deviation of the study results
Average ability duc- Data
ibility from the NIST Data is less than the reproducibility bounds.
Boiling point (K) at 1000 kPa 467.7 11.3 19.1 474.3 14.4.2 Bias for Distilled Water—The values listed in the
Normal Boiling point (K) at 371.2 2.0 3.5 371.6
101.325 kPa NIST column in 14.3.2 can be used as acceptable reference
Boiling point (K) at 10.0 kPa 308.3 3.2 3.6 308.5 values as defined in Practice E177. The deviation of the study
Vapor pressure (kPa) at 4.9 0.9 1.0 4.7
293.15 K
results from the NIST Data is less than the reproducibility
bounds.
14.3.2 Precision for Distilled Water:
ILS Repeat- Repro- NIST
Average ability duc- Data
15. Keywords
ibility
Boiling point (K) 450.9 3.5 10.0 453.1
15.1 Antoine equation; boiling pressure; boiling tempera-
at 1000 kPa ture; differential scanning calorimetry (DSC); differential ther-
Normal Boiling point (K) 373.6 1.0 2.9 373.2 mal analysis (DTA); vapor pressure
at 101.325 kPa

APPENDIX

(Nonmandatory Information)

X1. VAPOR PRESSURE OF WATER 5 kPa TO 2 MPa

TABLE X1.1 Continued

Pressure, Temperature, Pressure, Temperature, Pressure, Temperature,
TABLE X1.1 Vapor Pressure and Temperature MPa K MPa K MPa K
0.285 404.96 0.745 440.66 1.205 461.33
Pressure, Temperature, Pressure, Temperature, Pressure, Temperature,
0.295 406.13 0.755 441.21 1.215 461.71
MPa K MPa K MPa K
0.305 407.27 0.765 441.75 1.225 462.08
0.005 306.03 0.465 422.30 0.925 449.71 0.315 408.38 0.775 442.28 1.235 462.45
0.015 327.13 0.475 423.09 0.935 450.17 0.325 409.46 0.785 442.81 1.245 462.82
0.025 338.13 0.485 423.87 0.945 450.62 0.335 410.51 0.795 443.33 1.255 463.18
0.035 345.85 0.495 424.64 0.955 451.08 0.345 411.54 0.805 443.85 1.265 463.54
0.045 351.89 0.505 425.39 0.965 451.52 0.355 412.54 0.815 444.37 1.275 463.90
0.055 356.88 0.515 426.13 0.975 451.97 0.365 413.52 0.825 444.87 1.285 464.26
0.065 361.17 0.525 426.86 0.985 452.41 0.375 414.48 0.835 445.38 1.295 464.62
0.075 364.93 0.535 427.58 0.995 452.85 0.385 415.42 0.845 445.88 1.305 464.97
0.085 368.30 0.545 428.29 1.005 453.28 0.395 416.34 0.855 446.37 1.315 465.32
0.095 371.35 0.555 428.99 1.015 453.71 0.405 417.24 0.865 446.86 1.325 465.67
0.105 374.15 0.565 429.68 1.025 454.14 0.415 418.12 0.875 447.34 1.335 466.02
0.115 376.74 0.575 430.36 1.035 454.57 0.425 418.99 0.885 447.83 1.345 466.36
0.125 379.14 0.585 431.03 1.045 454.99 0.435 419.84 0.895 448.30 1.355 466.71
0.135 381.40 0.595 431.69 1.055 455.41 0.445 420.68 0.905 448.77 1.365 467.05
0.145 383.51 0.605 432.34 1.065 455.82 0.455 421.50 0.915 449.24 1.375 467.39
0.155 385.52 0.615 432.98 1.075 456.23 1.385 467.73 1.845 481.52
0.165 387.41 0.625 433.61 1.085 456.64 1.395 468.06 1.855 481.79
0.175 389.22 0.635 434.24 1.095 457.05 1.405 468.40 1.865 482.06
0.185 390.94 0.645 434.86 1.105 457.45 1.415 468.73 1.875 482.33
0.195 392.59 0.655 435.47 1.115 457.85 1.425 469.06 1.885 482.59
0.205 394.17 0.665 436.08 1.125 458.25 1.435 469.39 1.895 482.86
0.215 395.69 0.675 436.67 1.135 458.64 1.445 469.71 1.905 483.12
0.225 397.16 0.685 437.26 1.145 459.04 1.455 470.04 1.915 483.38
0.235 398.57 0.695 437.84 1.155 459.43 1.465 470.36 1.925 483.64
0.245 399.93 0.705 438.42 1.165 459.81 1.475 470.68 1.935 483.90
0.255 401.25 0.715 438.99 1.175 460.20 1.485 471.00 1.945 484.16
0.265 402.52 0.725 439.55 1.185 460.58 1.495 471.32 1.955 484.42
0.275 403.76 0.735 440.11 1.195 460.96 1.505 471.63 1.965 484.68

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 E1782 – 08

TABLE X1.1 Continued TABLE X1.1 Continued

Pressure, Temperature, Pressure, Temperature, Pressure, Temperature, Pressure, Temperature, Pressure, Temperature, Pressure, Temperature,
MPa K MPa K MPa K MPa K MPa K MPa K
1.515 471.95 1.975 484.93 1.695 477.35 . . . . . .
1.525 472.26 1.985 485.19 1.705 477.64 . . . . . .
1.535 472.57 1.995 485.44 1.715 477.93 . . . . . .
1.545 472.88 ... ... 1.725 478.21 . . . . . .
1.555 473.19 ... ... 1.735 478.49 . . . . . .
1.565 473.50 ... ... 1.745 478.77 . . . . . .
1.575 473.80 ... ... 1.755 479.05 . . . . . .
1.585 474.11 ... ... 1.765 479.33 . . . . . .
1.595 474.41 ... ... 1.775 479.61 . . . . . .
1.605 474.71 ... ... 1.785 479.89 . . . . . .
1.615 475.01 ... ... 1.795 480.16 . . . . . .
1.625 475.31 ... ... 1.805 480.44 . . . . . .
1.635 475.60 ... ... 1.815 480.71 . . . . . .
1.645 475.90 ... ... 1.825 480.98 . . . . . .
1.655 476.19 ... ... 1.835 481.25 . . . . . .
1.665 476.48 ... ...
1.675 476.78 ... ...
1.685 477.06 ... ...

REFERENCES

(1) Thompson, G. W., Chemical Reviews, Vol 38, 1946, pp. 1 – 39. International Temperature Scale of 1990 (ITS-90),” NIST-Technical
(2) Perrenot, B., de Valliere, P., and Widman, G., Journal of Thermal Note 1265.
Analysis, Vol 38, 1992, pp. 381 – 390. (5) Boublik, T., Fried, V., and Hala, E., The Vapor Pressures of Pure
(3) Contreras, M. D., Girela, F., and Parera, A., Thermochimica Acta, Vol Substances, Elsevier, New York, 1973.
219, 1993, pp. 167 – 172.
(4) Mangum, B. W., and Furukawa, G. T., “Guidelines for Realizing the (6) Willingham et al., J. Res. NBS, Vol 35, 1945, pp. 219 – 244.

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