Designation: D 611 – 82 (Reapproved 1998) An American National Standard

Designation: 2/91
AMERICAN SOCIETY FOR TESTING AND MATERIALS
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Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods for

Aniline Point and Mixed Aniline Point of Petroleum Products
and Hydrocarbon Solvents1
This standard is issued under the fixed designation D 611; 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.

These test methods were adopted as a joint ASTM-IP standard in 1964.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope D 1500 Test Method for ASTM Color of Petroleum Prod-

1.1 These test methods cover the determination of the ucts (ASTM Color Scale)2
aniline point of petroleum products and hydrocarbon solvents. D 2700 Test Method for Knock Characteristics of Motor
Method A is suitable for transparent samples with an initial and Aviation Fuels by the Motor Method3
boiling point above room temperature and where the aniline E 1 Specification for ASTM Thermometers4
point is below the bubble point and above the solidification
point of the aniline-sample mixture. Method B, a thin-film 3. Terminology
method, is suitable for samples too dark for testing by Method 3.1 Definitions:
A. Methods C and D are for samples that may vaporize 3.1.1 aniline point—the minimum equilibrium solution
appreciably at the aniline point. Method D is particularly temperature for equal volumes of aniline and sample.
suitable where only small quantities of sample are available. 3.1.2 mixed aniline point—the minimum equilibrium solu-
Method E describes a procedure using an automatic apparatus tion temperature of a mixture of two volumes of aniline, one
suitable for the range covered by Methods A and B. volume of sample, and one volume of n-heptane of specified
1.2 These test methods also cover the determination of the purity.
mixed aniline point of petroleum products and hydrocarbon
solvents having aniline points below the temperature at which 4. Summary of Test Methods
aniline will crystallize from the aniline-sample mixture. 4.1 Specified volumes of aniline and sample, or aniline and
1.3 This standard does not purport to address all of the sample plus n-heptane, are placed in a tube and mixed
safety concerns, if any, associated with its use. It is the mechanically. The mixture is heated at a controlled rate until
responsibility of the user of this standard to establish appro- the two phases become miscible. The mixture is then cooled at
priate safety and health practices and determine the applica- a controlled rate and the temperature at which two phases
bility of regulatory limitations prior to use. Specific precau- separate is recorded as the aniline point or mixed aniline point.
tionary statements are given in Sections 7.1 and 7.3.
5. Significance and Use
2. Referenced Documents 5.1 The aniline point (or mixed aniline point) is useful as an
2.1 ASTM Standards: aid in the characterization of pure hydrocarbons and in the
D 1015 Test Method for Freezing Points of High-Purity analysis of hydrocarbon mixtures. Aromatic hydrocarbons
Hydrocarbons2 exhibit the lowest, and paraffins the highest values. Cyclopar-
D 1217 Test Method for Density and Relative Density affins and olefins exhibit values that lie between those for
(Specific Gravity) of Liquids by Bingham Pycnometer2 paraffins and aromatics. In homologous series the aniline
D 1218 Test Method for Refractive Index and Refractive points increase with increasing molecular weight. Although it
Dispersion of Hydrocarbon Liquids2 occasionally is used in combination with other physical prop-
erties in correlative methods for hydrocarbon analysis, the
1
These test methods are under the jurisdiction of ASTM Committee D-2 on aniline point is most often used to provide an estimate of the
Petroleum Products and Lubricantsand are the direct responsibility of D02.04on aromatic hydrocarbon content of mixtures.
Hydrocarbon Analysis.
Current edition approved Aug. 27, 1982. Published January 1983. Originally
published as D 611 – 41 T. Last previous edition D 611 – 77. 3
2 Annual Book of ASTM Standards, Vol 05.04.
Annual Book of ASTM Standards, Vol 05.01. 4
Annual Book of ASTM Standards, Vol 14.03.

1
 D 611
6. Apparatus
taken to avoid contamination from atmospheric moisture (Note 2). It is
6.1 For details of the aniline point apparatus required for believed that under these conditions the aniline will remain unchanged
each method see: for a period exceeding 6 months.
Annex A1 for Method A
Annex A2 for Method B
7.2 Calcium Sulfate, anhydrous.
Annex A3 for Method C 7.3 n-Heptane (Warning—See Note 7), conforming to the
Annex A4 for Method D requirements listed in Table 1.5
Annex A5 for Method E
NOTE 7—Warning: Flammable. Harmful if inhaled. See Annex A6.1.
NOTE 1—Alternative apparatus may be used, such as the U-tube
method for dark oils, provided it has been shown to give results of the 8. Sample
same precision and accuracy as those described in the Annexes.
8.1 Dry the sample by shaking vigorously for 3 to 5 min
6.2 Heating and Cooling Bath—A suitable air bath, a
with about 10 volume % of a suitable drying agent such as
nonvolatile, transparent liquid bath, or an infrared lamp (250
anhydrous calcium sulfate or anhydrous sodium sulfate. Re-
to 375 W), provided with means for controlling the rate of
duce the viscosity of viscous samples by warming to a
heating.
temperature below that which would cause the loss of light
NOTE 2—Water should not be used as either a heating or cooling ends or the dehydration of the drying agent. Remove any
medium since aniline is hygroscopic and moist aniline will give suspended drying agent by use of a centrifuge or by filtration.
erroneous test results. For example, the aniline point of the n-heptane Heat samples containing separated wax until they are homo-
reagent as measured with aniline containing 0.1 volume % water is
approximately 0.5°C (0.9°F) higher than that measured with dry aniline. geneous and keep heated during filtration or centrifugation to
If the aniline point is below the dew point of the atmosphere, pass a slow ensure against separation of wax. When suspended water is
stream of dry inert gas into the aniline point tube to blanket the aniline- visibly present and the sample material is known to dissolve
sample mixture. less than 0.03 mass % of water, the use of a centrifuge for the
6.3 Thermometers, having the following ranges and con- removal of suspended water is an acceptable procedure.
forming to the requirements of the designated ASTM or IP
specification: 9. Procedure for Aniline Point

ASTM
9.1 The following methods, to be used as applicable, are
Range IP
(Specification E 1) covered as follows:
9.1.1 Method A, described in detail in Annex A1, is appli-
−38 to + 42°C (−36.5 to + 107.5°F) 33C, 33F 20C
25 to 105°C (77 to 221°F) 34C, 34F 21C
cable to clear samples or to samples not darker than No. 6.5
90 to 170°C (194 to 338°F) 35C, 35F 59C ASTM color, as determined by Test Method D 1500, having
6.4 Pipets, with capacities of 10 6 0.04 mL, 5 6 0.02 initial boiling points well above the expected aniline point.
mL, the latter equipped with a long, fine tip. Provide a 9.1.2 Method B, described in detail in Annex A2, is appli-
rubber suction bulb for use with pipets when measuring cable to light-colored samples, moderately dark samples, and
aniline. to very dark samples. It is suitable for samples that are too
6.5 Balance—A laboratory balance sensitive to 0.01 g, dark to be tested by Method A.
suitable for weighing the tube and sample when the sample 9.1.3 Method C, described in detail in Annex A3, is appli-
cannot be pipetted conveniently. cable to clear samples or to samples not darker than No. 6.5
6.6 Safety Goggles. ASTM color, as determined by Test Method D 1500, having
6.7 Plastic Gloves, impervious to aniline. initial boiling points sufficiently low as to give incorrect
aniline point readings by Method A, for example, aviation
7. Reagents gasoline.
7.1 Aniline (Warning—See Note 3.) Dry chemically pure 9.1.4 Method D, described in detail in Annex A4, is appli-
aniline over potassium hydroxide pellets, decant, and distill cable to the same type of sample as Method C. It is
fresh on the day of use, discarding the first and last 10 %. particularly useful when only limited quantities of sample are
Aniline thus prepared when tested with n-heptane according to available.
Section 9 shall give an aniline point of 69.3 6 0.2°C (156.7 6
0.4°F) as determined from the average of two independent 5
These requirements for n-heptane are identical, except for tetraethyl lead, with
tests having a difference of not more than 0.1°C (0.2°F). those prescribed in the 1987 Annual Book of ASTM Standards, Vol 05.04.

NOTE 3—Warning: Aniline should not be pipetted directly by mouth TABLE 1 Requirements for n-Heptane
because of its extreme toxicity. Aniline is also toxic by absorption through
the skin even in very small quantities, and should be handled with great ASTM
caution. Method
NOTE 4—For routine purposes the distillation process is not mandatory ASTM Motor Octane Number 0.0 6 0.2 D 2700
provided the aniline meets the requirements of the test with n-heptane. Density at 20°C, g/mL 0.68380 6 0.00015 D 1217
NOTE 5—The aniline point of aniline and n-heptane determined with Refractive index, Dn 20°C 1.38770 6 0.00015 D 1218
Freezing point, °C −90.710 min D 1015
automatic apparatus (Method E) shall be 69.3 6 0.2°C (156.7°F 6 0.4°F) aniline may be distilled as Distillation, 50 % recovered at
when corrected in accordance with the equation in Section A5.2.1 described in 7.1, collecting the 1.013 bar (760 mm Hg), °C Differential,
NOTE 6—As an alternative to distilling the aniline on the day of use, distillate in 80 % recovered minus
the 20 % recovered, °C

2
 D 611
98.427 6 0.025 A
0.020 max
ampoules, sealing the ampoules under vacuum or dry nitrogen, and A
For equipment and method used, see Journal of Research, National Institute of
storing in a cool dark place for future use. In either case, rigid precaution Standards and Technology, Vol 44, No. 3, 1950, pp. 309 and 310 (RP2079).
must be

3
 D 611
9.1.5 Method E is applicable when using automatic appa-
ratus in accordance with the instructions in Annex A5. the normal and correct operation of the test method, exceed
the following values only in one case in twenty:
10. Procedure for Mixed Aniline Point Repeatability
10.1 This procedure is applicable to samples having aniline
Aniline point of:

points below the temperature at which aniline crystallizes Clear, light-colored samples 0.16°C (0.3°F)
Moderately dark to very dark samples 0.3°C
from the mixture. Pipet 10 mL of aniline (Warning: See Note (0.6°F)A
3), 5 mL of sample, and 5 mL of n-heptane into a Mixed aniline point of:
Clear, light-colored samples 0.16°C
clean, dry (0.3°F)A Moderately dark to very dark samples 0.3°C (0.6°F)A
apparatus. Determine the aniline point of the mixture by
Method A or B as described in Annex A1 or Annex A2. A
Not determined from recent cooperative tests; however, the ratios with those
given in the 1953 version are believed to apply.
11. Report 12.1.2 Reproducibility—The difference between two single
11.1 If the range of three successive observations of the and independent results, obtained by different operators,
aniline point temperature is not greater than 0.1°C (0.2°F) for work- ing in different laboratories on identical test material,
light-colored samples or 0.2°C (0.4°F) for dark samples, would in the long run, in the normal and correct operation of
report the average temperature of these observations, corrected the test method, exceed the following values only in one case
for thermometer calibration errors, to the nearest 0.05°C in twenty:
(0.1°F) as the aniline point. 12.2 Bias—A statement of bias is now being developed by
11.2 If such a range is not obtained after five observations, the subcommittee.
repeat the test using fresh quantities of aniline and sample in a Reproducibility

clean, dry apparatus, and if consecutive temperature observa- Aniline point of:
tions show a progressive change, or if the range of Clear, light-colored samples 0.5°C (0.9°F)
Moderately dark to very dark samples 1.0°C (1.8°F)A
observations is greater than the repeatability given in 12.1, Mixed aniline point of:
report the method as being inapplicable. Clear, light-colored samples 0.7°C (1.3°F)A
Moderately dark to very dark samples 1.0°C (1.8°F)A
12. Precision and Bias
A
Not determined from recent cooperative tests; however, the ratios with those
12.1 The precision of these test methods as obtained by given in the 1953 version are believed to apply.
statistical examination of interlaboratory test results is as 12.3 The precision of this test was not obtained in accor-
follows: dance with Committee D-2 Research Report RR:D02-1007,
12.1.1 Repeatability—The difference between successive “Manual on Determining Precision Data for ASTM Methods
test results (two average temperatures obtained in a series of on Petroleum Products and Lubricants.”
observations as described in Section 11 obtained by the same
13. Keywords
operator with the same apparatus under constant operating
conditions on identical test material, would in the long run, in 13.1 aniline point; aromatics; mixed aniline point

ANNEXES

(Mandatory Information)

A1. METHOD A

A1.1 Apparatus diameter shall be used as a guide for the stirrer. Any suitable
A1.1.1 The apparatus shown in Fig. A1.1 shall consist of mechanical device for operating the stirrer as specified is an
the following: approved
A1.1.1.1 Test Tube, approximately 25 mm in diameter and
150 mm in length, made of heat-resistant glass.
A1.1.1.2 Jacket, approximately 37 to 42 mm in diameter
and 175 mm in length, made of heat-resistant glass.
A1.1.1.3 Stirrer, manually operated, metal, approximately 2
mm in diameter (14 B&S gage) metal wire as shown in Fig.
A1.1. A concentric ring shall be at the bottom, having a
diameter of approximately 19 mm. The length of the stirrer to
a right-angle bend shall be approximately 200 mm. The
right-angle bend shall be approximately 55 mm long. A glass
sleeve approximately 65 mm in length of 3-mm inside
4
 D 611
alternative for the manual operation.

A1.2 Procedure
A1.2.1 Clean and dry the apparatus. Pipet 10 mL of
aniline (Warning— see 7.1) and 10 mL of the dried sample
(8.1) into the test tube fitted with stirrer and thermometer. If
the material is too viscous for pipetting, weigh to the nearest
0.01 g a quantity of the sample corresponding to 10 mL at
room temperature. Center the thermometer in the test tube so
that the immersion mark is at the liquid level, making sure
that the thermometer bulb does not touch the side of the tube.
Center the test tube in the jacket tube. Stir the mixture rapidly
using a 50-mm (2-in.) stroke, avoiding the introduction of air
bubbles.
A1.2.2 If the aniline-sample mixture is not miscible at
room temperature, apply heat directly to the jacket tube so
that the temperature rises at a rate of 1 to 3°C (2 to
5°F)/min by

5
 D 611

FIG. A1.1 Aniline Point Apparatus (Method A)

removing or reducing the heat source until complete

miscibility is obtained. Continue stirring and allow the mixture is so cloudy as to obscure the thermometer bulb in reflected light.
to cool at a rate of 0.5 to 1.0°C (1.0 to 1.8°F)/min. Continue A1.2.3 If the aniline-sample mixture is completely miscible
cooling to a temperature of 1 to 2°C (2.0 to 3.5°F) below the at room temperature, substitute a non-aqueous cooling bath for
first appearance of turbidity, and record as the aniline point the the heating source, allow to cool at the rate specified in A1.2.2
temperature at which the mixture suddenly becomes cloudy and determine the aniline point as described.
throughout (Note A1.1). This temperature, and not the tem-
A1.2.4 Repeat the observation of aniline point temperature
perature of separation of small amounts of material, is the
by heating and cooling repeatedly until a report as directed in
minimum equilibrium solution temperature.
Section 11 can be made.
NOTE A1.1—The true aniline point is characterized by a turbidity that

A2. METHOD B

A2.1 Apparatus 3.5°F)/min until the aniline point has just been passed, as
A2.1.1 Thin-Film Apparatus, made of heat-resistant glass denoted by a definite, sudden brightening of the lamp filament,
and stainless steel, conforming to the dimensions given in Fig. and by the disappearance of the more or less opalescent
A2.1. A suggested assembly is shown in Fig. A2.2. condition of the film (Note A2.1). Discontinue heating and
A2.2 Procedure adjust the lamp voltage so that the filament appears clear and
distinct but not uncomfortably bright to the eye. Adjust the
A2.2.1 Clean and dry the apparatus. Pipet 10 mL of aniline
temperature of the bath so that the sample-aniline mixture
(Warning— see Note 3) and 10 mL of the dried sample (8.1)
into the tube fitted with pump-stirrer and thermometer. If the cools at a rate of 0.5 to 1.0°C (1.0 to 1.8°F)/min and note the
material is too viscous for pipetting, weigh to the nearest 0.01 appearance of the film and light filament. Record as the aniline
g a quantity of sample corresponding to 10 mL at room point the temperature at which a second phase appears as
temperature. Place the thermometer in the tube so that the evidenced by the reappearance of the opalescent condition of
contraction chamber is below the liquid level and so that the the film (usually causing a halo to appear around the lamp
mercury bulb does not touch the side of the tube. Assemble filament) or by a sudden dimming of the lamp filament, or
the apparatus as shown in Fig. A2.2. both. At temperatures above the aniline point the edges of the
A2.2.2 Adjust the speed of the pump to produce a continu- light filament appear clear and distinct. At the aniline point
ous stream of the oil-aniline mixture in the form of a thin film tempera- ture a halo or haze forms around the filament,
flowing over the light well. With extremely dark oils, operate replacing the distinct lines of the filament edge with lines that
the pump slowly and lower it so that the delivery tube nearly appear cloudy or hazy in appearance. Further darkening of the
touches the top of the light well, so as to obtain a continuous cloud over the filament occurs at lower temperature, but is not
film thin enough to permit observation of the aniline point. to be confused with the aniline point.
Adjust the voltage on the lamp until just enough light is given
NOTE A2.1—For those making the test for the first time, the following
for the filament to be visible through the film. Raise the procedure may be helpful: Make preliminary operational adjustments and
temperature of the mixture at a rate of 1 to 2°C (2.0 to tests using a colorless sample-aniline mixture, and observing changes
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 D 611

FIG. A2.1 Details of Aniline Point Thin-Film Apparatus (Method B)

FIG. A2.2 Assembly of Thin-Film Apparatus (Method B)

taking place in the body of the liquid and film. Make rough tests with
dark oils to become familiar with the appearance of the film and light by heating and cooling repeatedly until a report as directed in
source as the mixture passes from the clear state above the aniline point, Section 11 can be made.
to the translucent state below. If the sample is such that there is difficulty
in observing the exact point of the phase change, make experiments with
the sample, using various intensities of light and paying particular
attention to the appearance of the light in the immediate vicinity of the
lamp filament.
A2.2.3 Repeat the observation of aniline point temperature

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A3. METHOD C

A3.1 Apparatus thermometer. The inner tube is held in the top of the aniline-
A3.1.1 Aniline-Point Tube, of heat-resistant glass, of the point tube by a tightly fitting stopper, and a clamp is provided
shape and dimensions shown in Fig. A3.1, and fitted internally to hold the stopper in position to prevent loss of vapor from
with a thin-walled glass thermometer tube, sealed at the lower the sample.
end. The latter tube accommodates a tight-fitting cork stopper
NOTE A3.1—Any other suitable arrangement, such as a screwed plastic
carrying the thermometer, the bulb of which rests on a cork gland carrying the thermometer, that will prevent the loss of vapor from
ring or disk placed at the bottom of the tube; the tube contains the apparatus, may be used. In such cases it may be possible to omit the
sufficient light transformer oil to cover the bulb of the thermometer tube and immerse the thermometer bulb in the aniline-
sample mixture.
A3.1.2 Guard, of stout metal gauze and surrounding the
aniline point tube. It should preferably be combined with the
clamp for holding the thermometer tube in place.

A3.2 Procedure
A3.2.1 Clean and dry the apparatus. Pipet 5 mL of aniline
(Note A3.2 Precaution see Note 3) and 5 mL of the dried
sample (8.1), both cooled to a temperature at which the sample
may be measured without loss of vapor. Close the tube by
means of the stopper and fit the thermometer tube centrally so
that the bottom is 5 mm from the bottom of the aniline point
tube. Clamp the stopper in position and attach the guard.
NOTE A3.2—Precaution: Put on goggles of safety glass and plastic
gloves impervious to aniline.
A3.2.2 Follow the procedure described in A1.2.2 and
A1.2.3 but mix the sample and aniline by shaking the tube. If
the rate of change of temperature is greater than 1°C
(2°F)/min when the aniline point is being approached, place
the tube in a jacket that has previously been warmed or cooled
to an appropriate temperature.
A3.2.3 Repeat the observation of aniline point by heating
and cooling repeatedly until a report as directed in Section 11
FIG. A3.1 Apparatus for Volatile Samples (Method C)
can be made.

A4. METHOD D

A4.1 Apparatus 10 mm from the center of the bulb.

A4.1.1 Bulb, 1.5 to 2.0-mL capacity, blown from heat-
resistant glass tubing, 5 mm in external diameter and 3 mm in NOTE A4.1—Precaution: Put on goggles of safety glass and plastic
internal diameter. gloves impervious to aniline.
A4.1.2 Guard, as for Method C. A4.2.2 Attach the bulb to the thermometer by rubber bands
so that the bulb is adjacent to the thermometer bulb. Attach the
A4.2 Procedure
mesh guard and follow the procedure described in A1.2.2 and
A4.2.1 Dry the bulb thoroughly in an oven at 105 6 5°C, A1.2.3 but mix the sample and aniline by shaking.
allow it to cool to room temperature, and charge it by means
A4.2.3 Repeat the observation of aniline point temperature
of the pipets with 0.5 mL of aniline (Warning— see Note 3)
and by heating and cooling repeatedly until a report as directed in
0.5 mL of the dried sample (8.1). Cool the mixture thoroughly Section 11 can be made.
and rapidly draw out and seal the open end of the bulb at about

8
 D 611

A5. METHOD E

A5.1 Apparatus more samples with aniline points in each of the ranges 43 to
A5.1.1 Automatic Aniline Point Apparatus, commercially 49°C (110 to 120°F), 60 to 66°C (140 to 150°F), and 77 to
available, using a modified thin film technique and direct 82°C (170 to 180°F). Calculate the constants A and B by the
heating of the sample-aniline mixture with electrical immer- least squares method by simultaneous solution of the
sion heater. Detection of change of sample turbidity at the following equations:
aniline point is by response of a photoelectric cell to
(~Xa! 5 NA 1 B(~Xc! (A5.2)
collimated light directed through the thin film of sample.
(~XaXc! 5 A(~Xc! 1 B(~Xc ! 2

A5.2 Procedure
where:
A5.2.1 Determine the automatic aniline point in accordance ((Xa) 5 sum of all aniline point data by automatic
with instructions provided with the apparatus. Correct the apparatus,
aniline point as follows: ((Xc) 5 sum of all aniline point data by either
Corrected aniline point 5 ~Xa 2 A!/B 2 Method A or B,

(A5.1) ((Xc ) 5 sum of the squares of all aniline point data

where: by either Method A or B,
Xa 5 automatic aniline point, and ((XaXc) 5 sum of the products of aniline points deter-
mined by either Method A or B and by
using
A and B 5 constants determined for each apparatus as the automatic apparatus for each sample, and
described in A5.2.2 N 5 number of samples.
NOTE A5.1—It has been established by cooperative tests that observed NOTE A5.2—Cooperative data were obtained from five laboratories for
aniline points determined by some automatic apparatus are lower than the five samples with aniline points in the range from 34 to 87°C (93 to
determinations by Methods A and B. The difference is greater for
188°F). Constants A and B were calculated for the composite data as 0.79
automatic apparatus when relatively high sample-cooling rates are used,
and 0.991 respectively. Although a minimum number of nine samples is
and increases as the aniline point increases.
specified in this method, constants A and B in the preceding equation may
A5.2.2 Determine the aniline point by either Method A or be obtained with a slightly greater precision if data for a larger number of
Method B and also using the automatic apparatus for three or samples are used.

A6. PRECAUTIONARY STATEMENT

A6.1 n-Heptane Use with adequate ventilation.

Warning—Flammable. Harmful if inhaled. Avoid prolonged breathing of vapor or spray mist.
Keep away from heat, sparks, and open flame.
Avoid prolonged or repeated skin contact.
Keep container closed.

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