United States Prevention, Pesticides EPA 712–C–96–034

Environmental Protection and Toxic Substances August 1996

Agency (TS–7101)

Product Properties
Test Guidelines
OPPTS 830.7220
Boiling Point/Boiling
Range
 INTRODUCTION
This guideline is one of a series of test guidelines that have been
developed by the Office of Prevention, Pesticides and Toxic Substances,
United States Environmental Protection Agency for use in the testing of
pesticides and toxic substances, and the development of test data that must
be submitted to the Agency for review under Federal regulations.
The Office of Prevention, Pesticides and Toxic Substances (OPPTS)
has developed this guideline through a process of harmonization that
blended the testing guidance and requirements that existed in the Office
of Pollution Prevention and Toxics (OPPT) and appeared in Title 40,
Chapter I, Subchapter R of the Code of Federal Regulations (CFR), the
Office of Pesticide Programs (OPP) which appeared in publications of the
National Technical Information Service (NTIS) and the guidelines pub-
lished by the Organization for Economic Cooperation and Development
(OECD).
The purpose of harmonizing these guidelines into a single set of
OPPTS guidelines is to minimize variations among the testing procedures
that must be performed to meet the data requirements of the U. S. Environ-
mental Protection Agency under the Toxic Substances Control Act (15
U.S.C. 2601) and the Federal Insecticide, Fungicide and Rodenticide Act
(7 U.S.C. 136, et seq.).
Final Guideline Release: This document is available from the U.S.
Government Printing Office, Washington, DC 20402 on The Federal Bul-
letin Board. By modem dial 202–512–1387, telnet and ftp:
fedbbs.access.gpo.gov (IP 162.140.64.19), internet: http://
fedbbs.access.gpo.gov, or call 202–512–0132 for disks or paper copies.
This guideline is available in ASCII and PDF (portable document format)
from the EPA Public Access Gopher (gopher.epa.gov) under the heading
‘‘Environmental Test Methods and Guidelines.’’

i
OPPTS 830.7220 Boiling point/boiling range.
(a) Scope—(1) Applicability. This guideline is intended to meet test-
ing requirements of both the Federal Insecticide, Fungicide, and
Rodenticide Act (FIFRA) (7 U.S.C. 136, et seq.) and the Toxic Substances
Control Act (TSCA) (15 U.S.C. 2601).
(2) Background. The source materials used in developing this har-
monized OPPTS test guideline are the OPPT guideline under 40 CFR
796.1220 Boiling Point/Boiling Range, OPP guideline 63–6 Boiling Point
(Pesticide Assessment Guidelines, Subdivision D: Product Chemistry, EPA
Report 540/9–82–018, October 1982) and OECD guideline 103 Boiling
Point/Boiling Range.
(b) Introduction. (1) Five methods used to determine the boiling
point are described in this guideline: The ebulliometric method is based
on the ASTM D 1120–72; the distillation method is based on the standards
ISO R 918 and the draft ISO DIS 4626, BS 4359/68, BS 4591/71, DIN
53171; the Siwoloboff method is based on JIS K 0064–1966; the photocell
detection method is based on the manufacturer’s manual under paragraph
(e)(4) of this guideline; the Dynamic Method was tested in the OECD
Laboratory Intercomparison Testing Programme, part I, 1979, for vapor
pressure determination.
(2) Qualifying statement. The methods and devices described in this
test guideline can be applied to liquids, provided that these do not undergo
chemical reaction at temperatures below the boiling point (e.g.,
autoxidation, rearrangement, degradation, etc.).
(c) Method. (1) Application and limits of test. The boiling point of
a substance is an environmentally relevant physical chemical property be-
cause it is important for identification purposes and is one factor influenc-
ing the states in which the substance will exist in the environment.
(2) The emphasis in this test guideline has been placed on the descrip-
tion of the method using photocell detection, because this method allows
the determination of melting as well as boiling points. Moreover, the meas-
urements can be performed automatically.
(3) The dynamic method has the advantage that it can also be applied
for the determination of vapor pressure and that it is not necessary to cor-
rect the boiling temperature to the normal pressure (101.325 kPa) because
the standard pressure can be adjusted during the measurement. However,
this method is not at present automated. (For a detailed description, see
OPPTS 830.7950 for the vapor pressure curve.
(4) Note: In the literature, different boiling points are sometimes
quoted for the same substance. These differences are due to such variables
as the dimension of the apparatus (for example, the fit of the thermometer),
the type of the thermometer, the stem correction, the pressure correction,

1
 and the accuracy of the pressure measurement. Therefore, the above-men-
tioned international and national standardized methods contain precise re-
quirements for these specified conditions.
(5) The influence of impurities on the determination of the boiling
point depends greatly upon the kind of impurity. Thus, the effect can be
considered if a highly volatile solvent is present in the sample. Impurities
will usually increase/decrease the measured boiling temperature.
(6) Definitions and units. (i) The standard boiling point is described
as the temperature at which the pressure of the saturated vapor of a liquid
is the same as the standard pressure.
(ii) The measured boiling point is dependent on the atmospheric pres-
sure. This dependence can be described quantitatively by the Clausius-
Clapeyron equation as follows:
log p = – ∆Hv/2.3 RT
where p is the vapor pressure of the substance, ∆Hv is its heat of vaporiza-
tion, and R is the universal molar gas constant, R = 8.31441 J mol-1K-1.
The temperature T is expressed in K).
(iii) The temperature at the boiling point (boiling temperature) is stat-
ed in K, with regard to the ambient pressure during the measurement. If
no pressure is given, the result refers to a standard pressure of 101.325
kPa.
(iv) Conversions:

Pressure Temperature

(units kPa) (units K)

100 kPa = 1 bar = 0.1 MPa1 ................................... t = T – 273.15

133 Pa = 1 mm Hg = 1 torr2 ................................... t in ° C, and T in K
1 ‘‘Bar’’ units are still permissible but not recommended.
2 The units mm Hg and torr are no longer permissible.

(A) At small deviations from the normal pressure (max. ± 5 kPa),

the boiling point temperatures are normalized to Tn by means of the fol-
lowing number-value-equation by Sidney-Young:

Tn = T + fT∆p

where:
∆p = (101.325 – p) (note sign)
p = barometer measurement in kPa
f T = rate of change of boiling point with pressure in K/kPa

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 T = measured boiling temperature in K
T n = boiling temperature corrected to normal pressure in K
(B) The temperature-correction factors f T and equations for their ap-
proximation are included in the international and national standards men-
tioned in paragraph (e)(2) of this guideline for many substances. For exam-
ple, the DIN 53171 method mentions the following rough corrections for
solvents included in paints under the following table 1:
Table 1.—Temperature Correction Factors fT

Temperature Correction factor Temperature Correction factor

(T,K) (fT, K/kPa) (T, K) (fT, K/kPa)

323.15 0.26 473.15 0.39

348.15 0.28 498.15 0.41
373.15 0.31 523.15 0.44
398.15 0.33 548.15 0.45
423.15 0.35 573.15 0.47
448.15 0.37

(C) A table of temperature-correction factors for organic solvents (see

ISO/DIS 4626 is included in the following table 2:
Table 2.—Temperature-Correction Factors for Organic Solvents (See ISO/DIS 4626)

Boiling Rate of change of boiling point with pressure

point °C
Thermometer
Product at
°C 101.325 K′ °C/0.1 kPa (°C/mbar) K °C/mmHg
kPa

Acetone ....................................... 39 56.1 0.029 0.039

Acetonitrile .................................. 40 81.6 0.032 0.043
Allyl alcohol ................................. 40 96.9 0.028 0.038
Allyl chloride ............................... 38 45.1 0.029 0.039
n-Amyl acetate ............................ 102 149.5 0.036 0.048
n-Amyl alcohol ............................ 41 138.0 0.031 0.041
Aromatic solvent naptha ............. 42 ........... 0.037 0.049
Benzene ...................................... 40 80.1 0.032 0.042
Isobutyl acetate .......................... 41 117.3 0.034 0.045
n-Butyl acetate ............................ 41 126.1 0.034 0.045
sec-Butyl acetate ........................ 40 112.4 0.034 0.045
Isobutyl alcohol ........................... 40 107.9 0.027 0.036
n-Butyl alcohol ............................ 40 117.7 0.028 0.037
sec-Butyl alcohol ........................ 40 99.5 0.026 0.035
tert-Butyl alcohol ......................... 40 82.5 0.025 0.033
p-tert-Butyl toluene ..................... 104 192.8 0.042 0.056
Cumene ...................................... 102 152.4 0.038 0.051
Cyclohexane ............................... 40 80.7 0.033 0.044
Cyclohexanone ........................... 102 155.7 0.038 0.051
Diacetone alcohol ....................... 102 169.2 0.038 0.050
Diisobutyl ketone ........................ 103 169.3 0.038 0.051
Diisobutylene .............................. 40 101.4 0.034 0.046
1,2-Dichloroethane ..................... 40 83.5 0.032 0.043
Dichloromethane ......................... 38 39.8 0.028 0.037
Diethyleneglycol .......................... 106 245.8 0.038 0.050
Diethylene glycol mono-n-butyl
ether ........................................ 105 230.4 0.038 0.051
Diethylene glycol monoethyl
ether ........................................ 104 201.9 0.036 0.048
Diethylene glycol monomethyl
ether ........................................ 104 193.8 0.035 0.047

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 Table 2.—Temperature-Correction Factors for Organic Solvents (See ISO/DIS 4626)—Continued

Boiling Rate of change of boiling point with pressure

point °C
Thermometer
Product at
°C 101.325 K′ °C/0.1 kPa (°C/mbar) K °C/mmHg
kPa

Dimethyl formamide .................... 102 153.0 0.033 0.044

Dipropylene glycol ...................... 106 232.8 0.038 0.051
Diisopropyl ether ......................... 39 68.3 0.031 0.041
Ethyl acetate ............................... 39 77.2 0.031 0.041
Ethyl alcohol ............................... 39 78.3 0.025 0.033
Ethyl benzene ............................. 41 136.2 0.037 0.049
Ethylene glycol ........................... 104 197.6 0.032 0.043
Ethylene glycol mono-n-butyl
ether ........................................ 103 171.2 0.035 0.047
Ethylene glycol monoethyl ether 102 135.1 0.033 0.044
Ethylene glycol monoethyl ether
acetate .................................... 102 156.3 0.035 0.046
Ethylene glycol monomethyl
ether ........................................ 41 124.5 0.031 0.041
Ethylene glycol monoisopropyl
ether ........................................ 102 142.8 0.033 0.044
2-Ethyl hexanol ........................... 104 184.8 0.034 0.046
Ethyl isoamyl ketone .................. 103 158.2 0.037 0.049
n-Hexyl acetate ........................... 103 171.6 0.038 0.050
Hexylene glycol .......................... 104 197.1 0.034 0.045
Isophorone .................................. 105 215.3 0.043 0.057
Mesityl oxide ............................... 41 129.8 0.035 0.047
4-Methoxy-4-methyl-2-pentanone 103 160.6 0.037 0.049
Methanol ..................................... 39 64.6 0.025 0.033
Methyl isoamyl acetate ............... 102 146.2 0.036 0.048
Methyl isoamyl ketone ................ 102 144.9 0.036 0.048
Methyl isobutyl carbinol .............. 41 131.8 0.031 0.041
Methyl isobutyl ketone ................ 41 116.2 0.035 0.046
Monoethanol amine .................... 103 170.7 0.030 0.040
Perchloroethylene ....................... 41 121.2 0.036 0.048
n-Propyl acetate ......................... 40 101.6 0.032 0.042
iso-Propyl acetate ....................... 40 88.5 0.031 0.041
n-Propyl alcohol .......................... 40 97.2 0.026 0.034
Isopropyl alcohol ......................... 40 82.3 0.025 0.033
Propylene glycol ......................... 104 187.6 0.032 0.043
Propylene oxide .......................... 38 34.3 0.027 0.036
Pyridine ....................................... 41 115.4 0.035 0.046
Toluene ....................................... 41 110.6 0.035 0.046
Triethylene glycol ........................ 107 287.6 0.038 0.050
Triethylene glycol monoethyl
ether ........................................ 106 255.4 0.038 0.051
Trichloroethylene ........................ 40 87.1 0.032 0.043
Vinyl acetate ............................... 39 72.7 0.030 0.040
White spirit .................................. 103 ........... 0.041 0.055
Xylene (isomer mixture) ............. 41 ........... 0.037 0.049
m-Xylene ..................................... 41 139.1 0.037 0.049
o-Xylene ...................................... 41 144.4 0.037 0.050
p-Xylene ...................................... 41 138.3 0.037 0.049

(7) Reference substances. The standard methods listed include speci-

fications for calibration and evaluation substances. These compounds need
not be employed in all cases when investigating a new substance. They
should primarily serve to calibrate the method from time to time and to
offer the chance to compare the results when another method is applied.

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 (8) Principle of the test methods. All methods for the determination
of the boiling point (boiling range) are based on the measurement of the
boiling temperature.
(i) Determination by use of the ebulliometer. See paragraphs (e)(1)
and (e)(4) of this guideline. Ebulliometers were originally developed for
the determination of molecular weight by boiling point elevation, but they
are also suited for exact boiling point measurements. A very simple appa-
ratus is described in ASTM D 1120–72. The liquid is heated in this appara-
tus under equilibrium conditions at atmospheric pressure until it boils. The
determined temperature of the liquid, corrected to standard pressure, is
the boiling point.
(ii) Dynamic method. See paragraph (e)(2) of this guideline. This
method measures the vapor recondensation temperature by means of a
thermocouple in the reflux while boiling. The pressure can be varied in
this method.
(iii) Distillation method for boiling point (and boiling range). This
method involves distillation of the liquid and measurement of the vapor
recondensation temperature and determination of the amount of distillate.
(iv) Method according to Siwoloboff. See paragraph (e)(2) of this
guideline. A sample is heated in a sample tube which is immersed in a
heat-bath liquid. A fused capillary, containing an air bubble in the lower
part, is dipped in the sample tube. The temperature at which a regular
string of bubbles escapes from the capillary or the temperature at which
the string of bubbles stops and the fluid suddenly starts rising in the cap-
illary (Siwoloboff under paragraph (e)(2) of this guideline) is determined.
(v) Photocell detection. See paragraph (e)(3) of this guideline. Using
the principle according to Siwoloboff. Measurements are automatic, the
rising bubbles being detected photo-electrically.
(9) Quality criteria. The different methods for the determination of
the boiling point (boiling range) are compared with regard to their use
and precision and possibility to standardize/automate in the following table
3:
Table 3.—Comparison of the Methods

Method of measurement Approximate accuracy Ability to standardize Automation

Ebulliometer ............................ ±1.4 K (up to 373 K) 1 ............. Existing standard ASTM D Difficult as yet
1120–72 1.
±2.5 K (above 373 K) 1
Dynamic method ..................... ±0.5 K ..................................... Possible .................................. Difficult
Distillation process (boiling ±0.5 K ..................................... Existing standards, e.g., ISO/ Difficult as yet
range). R 918, DIN 53171, BS
4591/17.
According to Siwoloboff .......... ±1K to ±2K .............................. Possible .................................. Automatic method exists (see
photocell detection)
Photocell detection ................. ±0.3 K (at 373 K) .................... Possible .................................. Measurement process works
automatically
Differential scanning ±0.5 K (up to 600 K) ............... Existing standard .................... Automatic method
calorimetry.

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 Table 3.—Comparison of the Methods—Continued

Method of measurement Approximate accuracy Ability to standardize Automation

±2.0 K (up to 1273 K) ASTM E537–76 exists

Differential thermal analysis ... ±0.5 K (up to 600 K) ............... Existing standard .................... Automatic method
±2.0 K (up to 1273 K) ASTM E537–76 exists
1 This accuracy is only valid for pure substances and for the simple device as, for example, described in ASTM D 1120–72; it
can be improved with more sophisticated ebulliometer devices.

(10) Description of the test procedures. The procedures of several of

the test methods have been established by various international and na-
tional standards mentioned above. Reference is made here to those stand-
ards which prescribe details of preparations, test conditions, and conduct
of the test.

(i) Ebulliometer. See ASTM D 1120–72, Standard Test Method for

Boiling Point of Engine Antifreezes, and reference under paragraph (e)(4)
of this guideline.

(ii) Dynamic method. See OPPTS 830.7950 for Vapour Pressure

Curve, Principle of the test methods. The boiling temperature observed
with an applied pressure of 101.325 kPa is recorded.

(iii) Distillation process (boiling range). See ISO/R 918, Test Method
for Distillation (Distillation Yield and Distillation Range); ISO 4626/1980,
Volatile Organic Liquids—Determination of Boiling Range of Organic
Solvents Used as Raw Materials; BS 4349/68, Method for Determination
of Distillation of Petroleum Products; BS 4591/71, Method for the Deter-
mination of Distillation Characteristics; DIN 53171, Lösungsmittel für
Anstrichstoffe, Bestimmung des Siedeverlaufes; DIN 51751, Prüfung
flüssiger Mineralkohlenwasserstoffe—Bestimmung des Siedeverlaufes.

(iv) Method according to Siwoloboff. (A) The sample is heated in

a melting point apparatus in a sample tube, with a diameter of approxi-
mately 5 mm in the following figure 1:

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 FIGURE 1—APPARATUS FOR THE DETERMINATION OF MELTING AND
BOILING POINT (JISK 0064–1966), WITH SPECIFICATIONS IN MILLIMETERS

(B) A capillary tube (boiling capillary) fused about 1 cm above the

lower end is placed in the sample tube. The level to which the test sub-
stance is filled is such that the fused section of the capillary is below
the surface of the liquid. The sample tube containing the boiling capillary

7
is fastened either to the thermometer with a rubber-band or is fixed with
a support from the side under the following figure 2:
FIGURE 2—PRINCIPLE ACCORDING TO SIWOLOBOFF

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 (C) The bath liquid is chosen according to boiling temperature. At
temperatures of up to 573 K sulfuric acid or silicon oil can be used; if
sulfuric acid is used, this liquid must be handled with extreme care. Liquid
paraffin may only be used up to 473 K. The heating of the bath liquid
should be adjusted to a temperature rise of 3 K/min at first. The bath
liquid must be stirred. At about 10 K below the expected boiling point,
the heating is reduced so that the rate of temperature rise is less than
1 K/min. When the boiling temperature is approached, bubbles begin to
emerge from the boiling capillary.

(D) The boiling point is reached when the string of bubbles stops
and fluid suddenly starts rising in the capillary. The corresponding ther-
mometer reading is the boiling temperature of the substance.

(E) In the modified principle, under the following figure 3, the boiling
point is determined in the melting point capillary which is stretched to
a fine point about 2 cm in length (A) and a small amount of the sample
is aspirated. The open end of the fine capillary is closed by melting, so
that a small air bubble is located at the end. When heated in the melting
point apparatus (B), the air bubble expands. The boiling point corresponds
to the temperature at which the substance plug reaches the level of the
surface of the bath liquid (C).
FIGURE 3—MODIFIED PRINCIPLE

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 (v) Photocell detection. (A) The sample is heated in a capillary tube
inside a heated metal block. A light beam is directed via suitable holes
in the block through the substance onto a precisely calibrated photocell.
During the increase of the sample temperature, single air bubbles emerge
from the boiling capillary. When the boiling temperature is reached, the
amount of bubbles increases immensely.
(B) This causes a change in the intensity of light, which is recorded
by a photocell and gives a stop signal to the digital indicator reading out
the temperature of a platinum resistance thermometer, located in the block.
(C) This method is especially useful because it allows determinations
below room temperature as low as 253.15 K (–20 °C) without any changes
in the apparatus. The instrument merely has to be placed in a cold room
or cooling bath. The exact execution of the boiling point determination
can be obtained from the instrument manual.
(vi) Differential scanning calorimetry. See ASTM E 537-76 and
OECD 103. Samples of the test substance and a reference material are
subjected to the same controlled temperature program. The difference in
energy input necessary to maintain identical temperatures in the substance
and the reference material is recorded. When the sample undergoes a tran-
sition involving a change in enthalpy (endothermic on boiling), that change
is indicated by a departure from the base line of the heat flow record.
(vii) Differential thermal analysis. See ASTM E 537-76 and OECD
103. The difference in temperature between the substance and a reference
material, which are both subjected to the same controlled temperature pro-
gram, are recorded. When the sample undergoes a transition involving a
change in enthalpy (endothermic in the case of boiling), that change is
indicated by a departure from the base line of the temperature record.
(11) General remarks. (i) The results obtained for mixtures or impure
samples are to be interpreted with care. With an impure sample, for in-
stance, the emergence of a low boiling component will be registered as
the boiling point. Repeated determinations with the same impure sample
can change the composition from measurement to measurement, due to
the volatilization of low boiling components: continously increasing values
are obtained in these circumstances.
(ii) Liquids with a tendency to superheat can yield incorrect results.
The values obtained are usually too high. This happens more frequently
at higher temperatures. Distillation methods or the dynamic vapor pressure
method are more suitable for these types of compound.
(d) Data and reporting—(1) Treatment of results. (i) The boiling
point to be determined should be a mean of at least two measurements,
which are in the range of approximate accuracy indicated in table 2 under

10
paragraph (c)(9) of this guideline. If determinations are not reproducible,
other methods should be considered (see General remarks, above).
(ii) The measured boiling points and their mean should be stated in
K, and the pressure(s) at which the measurement(s) was (were) made
should be recorded in kPa. Where a test substance boils over a temperature
range, this range should be provided. The measured values should also
be corrected to standard pressure. Estimates of accuracy should be pro-
vided for all results.
(iii) The method used should be indicated, including any deviations
from procedures described in this test guideline.
(2) [Reserved]
(e) Literature references. The following references should be con-
sulted for additional background material on this test guideline.
(1) Kienitz, H. Methoden der Organischen Chemie ed. Houben-Weyl,
Vol. 2, (Georg Thieme Verlag, Stuttgart, 1953, pp. 815–821.
(2) Test Guideline 104 for Vapour Pressure Curve, A 80/5
Umweltbundesamt, Berlin (1980).
(3) Siwoloboff, A. Berichte-Deutsche Chemische Gesellschaft 19: 795
(1886).
(4) Manual of Apparatus FP 5+FP 51, FP 52 and FP 53, Mettler
Instrumente AG, CH–8606 Greifensee-Zürich, Switzerland.
(5) European Pharmacopoeia, 1:75 (1974).
(6) Organization for Economic Cooperation and Development, Guide-
lines for The Testing of Chemicals, OECD 103, Boiling Point/Boiling
Range, OECD, Paris, France.
(7) ASTM Standard Method E 537-76, Standard Method for Assess-
ing the thermal stability of Chemicals by Methods of Differential Thermal
Analysis (ASTM Annual Index, latest edition).

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