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

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

Designation: D611 − 12 (Reapproved 2016)

Designation: 2/98

Standard Test Methods for

Aniline Point and Mixed Aniline Point of Petroleum Products
and Hydrocarbon Solvents1
This standard is issued under the fixed designation D611; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope and/or mercury containing products into your state or country

may be prohibited by law.
1.1 These test methods cover the determination of the
aniline point of petroleum products and hydrocarbon solvents. 1.5 This standard does not purport to address all of the
Test Method A is suitable for transparent samples with an safety concerns, if any, associated with its use. It is the
initial boiling point above room temperature and where the responsibility of the user of this standard to establish appro-
aniline point is below the bubble point and above the solidifi- priate safety and health practices and determine the applica-
cation point of the aniline-sample mixture. Test Method B, a bility of regulatory limitations prior to use. Specific warning
thin-film method, is suitable for samples too dark for testing by statements are given in Section 7.
Test Method A. Test Methods C and D are for samples that may 2. Referenced Documents
vaporize appreciably at the aniline point. Test Method D is
particularly suitable where only small quantities of sample are 2.1 ASTM Standards:2
available. Test Method E describes a procedure using an D1500 Test Method for ASTM Color of Petroleum Products
automatic apparatus suitable for the range covered by Test (ASTM Color Scale)
Methods A and B. E1 Specification for ASTM Liquid-in-Glass Thermometers
1.2 These test methods also cover the determination of the 3. Terminology
mixed aniline point of petroleum products and hydrocarbon 3.1 Definitions:
solvents having aniline points below the temperature at which 3.1.1 aniline point, n—the minimum equilibrium solution
aniline will crystallize from the aniline-sample mixture. temperature for equal volumes of aniline and sample.
1.3 The values stated in SI units are to be regarded as 3.1.2 mixed aniline point, n—the minimum equilibrium
standard. No other units of measurement are included in this solution temperature of a mixture of two volumes of aniline,
standard. one volume of sample, and one volume of n-heptane of
1.4 WARNING—Mercury has been designated by many specified purity.
regulatory agencies as a hazardous material that can cause 4. Summary of Test Method
central nervous system, kidney and liver damage. Mercury, or
its vapor, may be hazardous to health and corrosive to 4.1 Specified volumes of aniline and sample, or aniline and
materials. Caution should be taken when handling mercury and sample plus n-heptane, are placed in a tube and mixed
mercury containing products. See the applicable product Ma- mechanically. The mixture is heated at a controlled rate until
terial Safety Data Sheet (MSDS) for details and EPA’s the two phases become miscible. The mixture is then cooled at
website—http://www.epa.gov/mercury/faq.htm—for addi- a controlled rate and the temperature at which two phases
tional information. Users should be aware that selling mercury separate is recorded as the aniline point or mixed aniline point.
5. Significance and Use
5.1 The aniline point (or mixed aniline point) is useful as an
1
These test methods are under the jurisdiction of ASTM Committee D02 on aid in the characterization of pure hydrocarbons and in the
Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility
of D02.04.0D on Physical and Chemical Methods.
2
Current edition approved Oct. 1, 2016. Published November 2016. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1941. Last previous edition approved in 2012 as D611 – 12. DOI: contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
10.1520/D0611-12R16. Standards volume information, refer to the standard’s Document Summary page on
These test methods were adopted as a joint ASTM-IP standard in 1964. the ASTM website.

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

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 D611 − 12 (2016)
analysis of hydrocarbon mixtures. Aromatic hydrocarbons aniline shall be sufficiently pure such that when tested with
exhibit the lowest, and paraffins the highest values. Cyclopar- n-heptane according to Section 9, it shall give an aniline point
affins and olefins exhibit values that lie between those for of 69.3 °C 6 0.2 °C (156.7 °F 6 0.4 °F) as determined from
paraffins and aromatics. In homologous series the aniline the average of two independent tests having a difference of not
points increase with increasing molecular weight. Although it more than 0.1 °C (0.2 °F). If the aniline point of heptane is
occasionally is used in combination with other physical prop- higher than this specification, the aniline may be dried by
erties in correlative methods for hydrocarbon analysis, the distillation, where the first and last 10 % are discarded. If the
aniline point is most often used to provide an estimate of the aniline point is lower, water may be added until the aniline
aromatic hydrocarbon content of mixtures. meets the specification.
6. Apparatus NOTE 3—It is estimated that approximately 400 ppm to 1400 ppm of
water in aniline is required to meet the heptane specification.
6.1 For details of the aniline point apparatus required for NOTE 4—As an alternative to distilling the aniline on the day of use, the
each method see: aniline may be distilled as described in 7.1, collecting the distillate in
ampoules, sealing the ampoules under vacuum or dry nitrogen, and storing
Annex A1 for Test Method A
Annex A2 for Test Method B
in a cool dark place for future use. Alternatively, distillate may be stored
Annex A3 for Test Method C under dry nitrogen in a glass bottle or in single use ampoules kept in a
Annex A4 for Test Method D cool, dark place. In either case, rigid precaution must be taken to avoid
Annex A5 for Test Method E contamination from atmospheric moisture (Note 2). It is believed that
under these conditions the aniline will remain unchanged for a period
NOTE 1—Alternative apparatus may be used, such as the U-tube method exceeding 6 months.
for dark oils, provided it has been shown to give results of the same
precision and accuracy as those described in the annexes. 7.2 Calcium Sulfate, anhydrous.
6.2 Heating and Cooling Bath—A suitable air bath, a 7.3 n-Heptane, spectroscopic or HPLC grade. (Warning—
nonvolatile, transparent liquid bath, or an infrared lamp Flammable. Harmful if inhaled. Keep away from heat, sparks,
(250 W to 375 W), provided with means for controlling the and open flame. Keep container closed. Use with adequate
rate of heating. ventilation. Avoid prolonged breathing of vapor or spray mist.
Avoid prolonged or repeated skin contact.)
NOTE 2—Water should not be used as either a heating or cooling
medium since aniline is hygroscopic and moist aniline will give erroneous
test results. For example, the aniline point of the n-heptane reagent as 8. Sample
measured with aniline containing 0.1 % by volume water is approximately 8.1 Dry the sample by shaking vigorously for 3 min to
0.5 °C (0.9 °F) higher than that measured with dry aniline. If the aniline
point is below the dew point of the atmosphere, pass a slow stream of dry 5 min with about 10 % by volume of a suitable drying agent
inert gas into the aniline point tube to blanket the aniline-sample mixture. such as anhydrous calcium sulfate or anhydrous sodium
6.3 Thermometers, or other temperature sensing devices, sulfate. Reduce the viscosity of viscous samples by warming to
such as thermocouples or platinum resistance thermometers a temperature below that which would cause the loss of light
that cover the temperamental range of interest and can provide ends or the dehydration of the drying agent. Remove any
equivalent or better accuracy and precision, may be used in suspended drying agent by use of a centrifuge or by filtration.
place of the thermometers having the following ranges and Heat samples containing separated wax until they are homo-
conforming to the requirements of the designated ASTM or IP geneous and keep heated during filtration or centrifugation to
specification: ensure against separation of wax. When suspended water is
visibly present and the sample material is known to dissolve
ASTM
Range
(Specification E1)
IP less than 0.03 % by mass of water, the use of a centrifuge for
the removal of suspended water is an acceptable procedure.
−38 °C to + 42 °C (−36.5 °F 33C, 33F 20C
to + 107.5 °F)
25 °C to 105 °C (77 °F to 221 °F) 34C, 34F 21C
9. Procedure for Aniline Point
90 °C to 170 °C (194 °F to 338 °F) 35C, 35F 59C 9.1 The following methods, to be used as applicable, are
6.4 Pipets, or equivalent volume dispensing devices, ca- covered as follows:
pable of delivering volumes with capacities of 10 mL 6 9.1.1 Test Method A, described in detail in Annex A1, is
0.04 mL and 5 mL 6 0.02 mL, for use in the test. applicable to clear samples or to samples not darker than No.
6.5 Balance—A laboratory balance sensitive to 0.01 g, suit- 6.5 ASTM color, as determined by Test Method D1500, having
able for weighing the tube and sample when the sample cannot initial boiling points well above the expected aniline point.
be pipetted conveniently. 9.1.2 Test Method B, described in detail in Annex A2, is
applicable to light-colored samples, moderately dark samples,
6.6 Safety Goggles. and to very dark samples. It is suitable for samples that are too
6.7 Plastic Gloves, impervious to aniline. dark to be tested by Test Method A.
9.1.3 Test Method C, described in detail in Annex A3, is
7. Reagents applicable to clear samples or to samples not darker than No.
7.1 Aniline (Warning—Aniline should not be pipetted di- 6.5 ASTM color, as determined by Test Method D1500, having
rectly by mouth because of its extreme toxicity. Aniline is also initial boiling points sufficiently low as to give incorrect aniline
toxic by absorption through the skin even in very small point readings by Test Method A, for example, aviation
quantities, and should be handled with great caution.) The gasoline.

2
 D611 − 12 (2016)
9.1.4 Test Method D, described in detail in Annex A4, is conditions on identical test material, would in the long run, in
applicable to the same type of sample as Test Method C. It is the normal and correct operation of the test method, exceed the
particularly useful when only limited quantities of sample are following values only in one case in twenty:
available. Repeatability
9.1.5 Test Method E is applicable when using automatic Aniline point of:
apparatus in accordance with the instructions in Annex A5. Clear, light-colored samples 0.16 °C (0.3 °F)
Moderately dark to very dark samples 0.3 °C (0.6 °F)A
Mixed aniline point of:
10. Procedure for Mixed Aniline Point Clear, light-colored samples 0.16 °C (0.3 °F)A
Moderately dark to very dark samples 0.3 °C (0.6 °F)A
10.1 This procedure is applicable to samples having aniline
points below the temperature at which aniline crystallizes from A
Not determined from recent cooperative tests; however, the ratios with those
the mixture. Deliver 10 mL of aniline (Warning—See 7.1), given in the 1953 version are believed to apply.
5 mL of sample, and 5 mL of n-heptane into a clean, dry
apparatus. Determine the aniline point of the mixture by Test 12.1.2 Reproducibility—The difference between two single
Method A or B as described in Annex A1 or Annex A2. and independent results, obtained by different operators, work-
ing in different laboratories on identical test material, would in
11. Report the long run, in the normal and correct operation of the test
11.1 If the range of three successive observations of the method, exceed the following values only in one case in
aniline point temperature is not greater than 0.1 °C (0.2 °F) for twenty:
light-colored samples or 0.2 °C (0.4 °F) for dark samples, Reproducibility
report the average temperature of these observations, corrected Aniline point of:
Clear, light-colored samples 0.5 °C (0.9 °F)
for thermometer calibration errors, to the nearest 0.05 °C Moderately dark to very dark samples 1.0 °CA (1.8 °F)
(0.1 °F) as the aniline point. Mixed aniline point of:
Clear, light-colored samples 0.7 °C (1.3 °F)A
11.2 If such a range is not obtained after five observations, Moderately dark to very dark samples 1.0 °C (1.8 °F)A
repeat the test using fresh quantities of aniline and sample in a
A
clean, dry apparatus, and if consecutive temperature observa- Not determined from recent cooperative tests; however, the ratios with those
given in the 1953 version are believed to apply.
tions show a progressive change, or if the range of observations
is greater than the repeatability given in 12.1, report the test 12.2 Bias—Since there is no accepted reference material
method as being inapplicable. suitable for determining the bias for the procedure in these test
methods, bias has not been determined.
12. Precision and Bias
12.1 The precision of these test methods as obtained by 12.3 The precision of this test was not obtained in accor-
statistical examination of interlaboratory test results is as dance with Committee D02 Research Report RR:D02-1007,
follows: “Manual on Determining Precision Data for ASTM Methods
12.1.1 Repeatability—The difference between successive on Petroleum Products and Lubricants.”
test results (two average temperatures obtained in a series of
observations as described in Section 11 obtained by the same 13. Keywords
operator with the same apparatus under constant operating 13.1 aniline point; aromatics; mixed aniline point

ANNEXES

(Mandatory Information)

A1. TEST METHOD A

A1.1 Apparatus a right-angle bend shall be approximately 200 mm. The right-
angle bend shall be approximately 55 mm long. A glass sleeve
A1.1.1 The apparatus shown in Fig. A1.1 shall consist of the
approximately 65 mm in length of 3 mm inside diameter shall
following:
be used as a guide for the stirrer. Any suitable mechanical
A1.1.1.1 Test Tube, approximately 25 mm in diameter and device for operating the stirrer as specified is an approved
150 mm in length, made of heat-resistant glass. alternative for the manual operation.
A1.1.1.2 Jacket, approximately 37 mm to 42 mm in diam-
eter and 175 mm in length, made of heat-resistant glass. A1.2 Procedure
A1.1.1.3 Stirrer, manually operated, metal, approximately A1.2.1 Clean and dry the apparatus. Deliver 10 mL of
2 mm in diameter (14 B&S gage) metal wire as shown in Fig. aniline (Warning—See 7.1) and 10 mL of the dried sample
A1.1. A concentric ring shall be at the bottom, having a (8.1) into the test tube fitted with stirrer and thermometer. If the
diameter of approximately 19 mm. The length of the stirrer to material is too viscous for volumetric transfer, weigh to the

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 D611 − 12 (2016)

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

nearest 0.01 g a quantity of the sample corresponding to 10 mL point the temperature at which the mixture suddenly becomes
at room temperature. Center the thermometer in the test tube so cloudy throughout (Note A1.1). This temperature, and not the
that the immersion mark is at the liquid level, making sure that temperature of separation of small amounts of material, is the
the thermometer bulb does not touch the side of the tube. minimum equilibrium solution temperature.
Center the test tube in the jacket tube. Stir the mixture rapidly
using a 50 mm (2 in.) stroke, avoiding the introduction of air NOTE A1.1—The true aniline point is characterized by a turbidity that
bubbles. is so cloudy as to obscure the thermometer bulb in reflected light.

A1.2.2 If the aniline-sample mixture is not miscible at room A1.2.3 If the aniline-sample mixture is completely miscible
temperature, apply heat directly to the jacket tube so that the at room temperature, substitute a non-aqueous cooling bath for
temperature rises at a rate of 1 °C to 3 °C (2 °F to 5 °F) ⁄min by the heating source, allow to cool at the rate specified in A1.2.2
removing or reducing the heat source until complete miscibility and determine the aniline point as described.
is obtained. Continue stirring and allow the mixture to cool at
A1.2.4 Repeat the observation of aniline point temperature
a rate of 0.5 °C to 1.0 °C (1.0 °F to 1.8 °F) ⁄min. Continue
by heating and cooling repeatedly until a report as directed in
cooling to a temperature of 1 °C to 2 °C (2.0 °F to 3.5 °F)
Section 11 can be made.
below the first appearance of turbidity, and record as the aniline

A2. TEST METHOD B

A2.1 Apparatus A2.2.2 Adjust the speed of the pump to produce a continu-
ous stream of the oil-aniline mixture in the form of a thin film
A2.1.1 Thin-Film Apparatus, made of heat-resistant glass
flowing over the light well. With extremely dark oils, operate
and stainless steel, conforming to the dimensions given in Fig.
the pump slowly and lower it so that the delivery tube nearly
A2.1. A suggested assembly is shown in Fig. A2.2. touches the top of the light well, so as to obtain a continuous
A2.2 Procedure film thin enough to permit observation of the aniline point.
Adjust the voltage on the lamp until just enough light is given
A2.2.1 Clean and dry the apparatus. Deliver 10 mL of for the filament to be visible through the film. Raise the
aniline (Warning—See 7.1) and 10 mL of the dried sample temperature of the mixture at a rate of 1 °C to 2 °C (2.0 °F to
(8.1) into the tube fitted with pump-stirrer and thermometer. If 3.5 °F) ⁄min until the aniline point has just been passed, as
the material is too viscous for volumetric transfer, weigh to the denoted by a definite, sudden brightening of the lamp filament,
nearest 0.01 g a quantity of sample corresponding to 10 mL at and by the disappearance of the more or less opalescent
room temperature. Place the thermometer in the tube so that the condition of the film (Note A2.1). Discontinue heating and
contraction chamber is below the liquid level and so that the adjust the lamp voltage so that the filament appears clear and
mercury bulb does not touch the side of the tube. Assemble the distinct but not uncomfortably bright to the eye. Adjust the
apparatus as shown in Fig. A2.2. temperature of the bath so that the sample-aniline mixture

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 D611 − 12 (2016)

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

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

cools at a rate of 0.5 °C to 1.0 °C (1.0 °F to 1.8 °F) ⁄min and darkening of the cloud over the filament occurs at lower
note the appearance of the film and light filament. Record as temperature, but is not to be confused with the aniline point.
the aniline point the temperature at which a second phase
NOTE A2.1—For those making the test for the first time, the following
appears as evidenced by the reappearance of the opalescent procedure may be helpful: Make preliminary operational adjustments and
condition of the film (usually causing a halo to appear around tests using a colorless sample-aniline mixture, and observe changes taking
the lamp filament) or by a sudden dimming of the lamp place in the body of the liquid and film. Make rough tests with dark oils
filament, or both. At temperatures above the aniline point the to become familiar with the appearance of the film and light source as the
edges of the light filament appear clear and distinct. At the mixture passes from the clear state above the aniline point, to the
translucent state below. If the sample is such that there is difficulty in
aniline point temperature a halo or haze forms around the observing the exact point of the phase change, make experiments with the
filament, replacing the distinct lines of the filament edge with sample, using various intensities of light and paying particular attention to
lines that appear cloudy or hazy in appearance. Further the appearance of the light in the immediate vicinity of the lamp filament.

5
 D611 − 12 (2016)
A2.2.3 Repeat the observation of aniline point temperature
by heating and cooling repeatedly until a report as directed in
Section 11 can be made.

A3. TEST METHOD C

A3.1 Apparatus sufficient light transformer oil to cover the bulb of the
A3.1.1 Aniline-Point Tube, of heat-resistant glass, of the thermometer. The inner tube is held in the top of the aniline-
shape and dimensions shown in Fig. A3.1, and fitted internally point tube by a tightly fitting stopper, and a clamp is provided
with a thin-walled glass thermometer tube, sealed at the lower to hold the stopper in position to prevent loss of vapor from the
end. The latter tube accommodates a tight-fitting cork stopper sample.
carrying the thermometer, the bulb of which rests on a cork NOTE A3.1—Any other suitable arrangement, such as a screwed plastic
ring or disk placed at the bottom of the tube; the tube contains gland carrying the thermometer, that will prevent the loss of vapor from
the apparatus, may be used. In such cases it may be possible to omit 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. Deliver 5 mL of aniline
(Warning—Put on goggles of safety glass and plastic gloves
impervious to aniline. Also see 7.1) 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.
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 (Test Method C) can be made.

A4. TEST METHOD D

A4.1 Apparatus means of the pipets with 0.5 mL of aniline (Warning—See

A4.1.1 Bulb, 1.5 mL to 2.0 mL capacity, blown from heat- 7.1) and 0.5 mL of the dried sample (8.1). Cool the mixture
resistant glass tubing, 5 mm in external diameter and 3 mm in thoroughly and rapidly draw out and seal the open end of the
internal diameter. bulb at about 10 mm from the center of the bulb. (Warning—
Put on goggles of safety glass and plastic gloves impervious to
A4.1.2 Guard, as for Test Method C.
aniline.)
A4.2 Procedure
A4.2.1 Dry the bulb thoroughly in an oven at 105 °C 6
5 °C, allow it to cool to room temperature, and charge it by

6
 D611 − 12 (2016)
A4.2.2 Attach the bulb to the thermometer by rubber bands A4.2.3 Repeat the observation of aniline point temperature
so that the bulb is adjacent to the thermometer bulb. Attach the by heating and cooling repeatedly until a report as directed in
mesh guard and follow the procedure described in A1.2.2 and Section 11 can be made.
A1.2.3 but mix the sample and aniline by shaking.

A5. TEST METHOD E

A5.1 Apparatus A5.2 Procedure

A5.1.1 Automatic Aniline Point Apparatus, commercially A5.2.1 Determine the automatic aniline point in accordance
available, using a modified thin film technique and direct with instructions provided with the apparatus.
heating of the sample-aniline mixture with electrical immer-
sion heater. Detection of change of sample turbidity at the
aniline point is by response of a photoelectric cell to collimated
light directed through the thin film of sample.

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