Designation: D 2074 – 07

Standard Test Methods for

Total, Primary, Secondary, and Tertiary Amine Values of
Fatty Amines by Alternative Indicator Method1
This standard is issued under the fixed designation D 2074; 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 prepared jointly by ASTM and the American Oil Chemists’ Society.

1. Scope 4. Apparatus
1.1 These alternative test methods cover the indicator pro- 4.1 Erlenmeyer Flasks, wide-mouth, alkali-resistant,
cedure for determining the total, primary, secondary, and borosilicate-glass, 250-mL capacity.
tertiary amine values of fatty amines. These procedures are not 4.2 Magnetic Stirrer, with an inert plastic-coated stirring
applicable to fatty amidoamines and fatty diamines. bar.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 5. Reagents
standard. 5.1 Purity of Reagents—Reagent grade chemicals shall be
1.3 This standard does not purport to address all of the used in all tests. Unless otherwise indicated, it is intended that
safety concerns, if any, associated with its use. It is the all reagents shall conform to the specifications of the Commit-
responsibility of the user of this standard to establish appro- tee on Analytical Reagents of the American Chemical Society,
priate safety and health practices and determine the applica- where such specifications are available.3 Other grades may be
bility of regulatory limitations prior to use. used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
2. Referenced Documents accuracy of the determination.
2.1 ASTM Standards: 2 5.2 Purity of Water—Unless otherwise indicated, references
D 1193 Specification for Reagent Water to water shall be understood to mean reagent water conforming
to Type II of Specification D 1193.
3. Terminology 5.3 Bromphenol Blue Indicator Solution—Dissolve 0.2 g of
3.1 Definitions: bromphenol blue in 100 mL of methanol, ethanol, or isopro-
3.1.1 primary amine value, n—the number of milligrams of panol.
potassium hydroxide (KOH) equivalent to the primary amine 5.4 Bromcresol Green Indicator Solution—Dissolve 0.1 g
basicity in 1 g of sample. of bromcresol green sodium salt in 100 mL of water.
3.1.2 secondary amine value, n—the number of milligrams 5.5 Chloroform (CHCl3).
of potassium hydroxide (KOH) equivalent to the secondary 5.6 Hydrochloric Acid, Standard Solution (0.1 N)—Add 17
amine basicity in 1 g of sample. mL of concentrated hydrochloric acid (HCl, sp gr 1.19) to 1000
3.1.3 tertiary amine value, n—the number of milligrams of mL of isopropyl alcohol in a 2-L volumetric flask. Make up to
potassium hydroxide (KOH) equivalent to the tertiary amine volume after cooling to room temperature. Standardize with
basicity in 1 g of sample. sodium carbonate using bromcresol green as the indicator.
3.1.4 total amine value, n—the number of milligrams of 5.7 Hydrochloric Acid, Standard Solution (0.2 N)—Add 34
potassium hydroxide (KOH) equivalent to the basicity in 1 g of mL of concentrated HCl (sp gr 1.19) to 1000 mL of isopropyl
sample. alcohol in a 2-L volumetric flask. Make up to volume after
cooling to room temperature. Standardize with sodium carbon-
1
ate using bromcresol green as the indicator.
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.33 on Polymers and Resins.
Current edition approved July 1, 2007. Published August 2007. Originally
3
approved in 1962. Last previous edition approved in 1998 as D 2074 – 92 (1998) Reagent Chemicals, American Chemical Society Specifications, American
which was withdrawn March 2007 and reinstated in July 2007. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.

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

1
 D 2074 – 07
5.8 Isopropyl Alcohol (99 %). NOTE 2—Instead of 0.2 N HCl, 0.1 N HCl may be used if the quantity
5.9 Phenyl Isothiocyanate. of tertiary amine is very low.
5.10 Salicylaldehyde. 8. Calculation
6. Procedure for Total Amine Value 8.1 Calculate the total amine value as follows:
6.1 Melt the sample, if it is not already liquid, in a water Total amine value 5 ~V 3 N 3 56.1!/S (1)
bath. Mix thoroughly, and accurately weigh 1 to 4 g to 0.1 mg
where:
into a 250 mL flask. Add 50 mL of alcohol and boil for 1 min V = HCl required for titration of the specimen (7.2), mL,
to drive off any free ammonia that may be present. Cool to N = normality of the HCl solution, and
room temperature. S = specimen weight used, g.
6.2 Add 5 drops of bromphenol blue indicator and titrate, 8.2 Calculate the amine value of secondary and tertiary
while swirling, with 0.2 N HCl to the yellow end point. amine groups as follows:
7. Procedure for Primary, Secondary, and Tertiary Titration S amine value of secondary and (2)
Amine Values tertiary amine groups 5 ~V 3 N 3 56.1!/S
7.1 Determine the specimen size as follows:
Specimen where:
Amine Value Weight, g V = HCl required for titration of the specimen (7.3), mL,
10 or less 5 N = normality of the HCl solution, and
Over 10 2 S = specimen weight used, g.
7.2 Melt the sample if it is not already liquid. Mix thor- 8.3 Calculate the amine value of tertiary amine groups as
oughly and accurately weigh the designated specimen size into follows:
two 150-mL beakers or 250-mL flasks. Mark them S and T. Titration T amine value of tertiary (3)
Add 50 mL of CHCl3 to each flask (or beaker) and boil for 1 amine groups 5 ~V 3 N 3 56.1!/S
min on a hot plate to drive off any free ammonia. Cool to room
temperature.
7.3 To beaker S add 3 mL of salicylaldehyde and allow to where:
V = HCl required for titration of the specimen (7.4), mL,
stand for 30 min. Add 1 mL of bromphenol blue indicator
N = normality of the HCl solution, and
solution and titrate while swirling (or by using the magnetic S = specimen weight used, g.
stirrer if beakers are used) with 0.2 N HCl to a yellow end point
8.4 Primary amine value equals total amine value minus the
(Note 1). The yellow may fade back to green upon standing,
amine value of the secondary and tertiary amine groups.
but this is to be disregarded if the yellow color is bright and the
8.5 Secondary amine value equals amine value of the
addition of another millilitre of 0.2 N HCl does not change the
secondary and tertiary amine groups minus the amine value of
yellow color.
tertiary amine groups.
NOTE 1—In the case of titrating the tertiary amine content of a primary 8.6 Tertiary amine value equals amine value of the tertiary
amine, it is advisable to use a microburet as the titration will be extremely amine groups.
small. Errors in titration are greatly magnified because of the high
molecular weights involved. 9. Precision and Bias
7.4 To flask T add 5 mL of phenyl isothiocyanate and allow 9.1 Precision and bias were not established at the time this
to stand for 30 min. Add 1 mL of bromphenol blue indicator test method was written. An effort is being made to obtain the
solution and titrate while swirling (or by using the magnetic precision and, if obtainable, it will be published in future
stirrer if beakers are used) with 0.2 N HCl to the yellow end revisions. This test method has been in use for many years, and
point (Note 1 and Note 2). The yellow may fade back to green its usefulness has been well established.
upon standing, but this may be disregarded if the yellow color
is bright and the addition of another millilitre of 0.2 N HCl 10. Keywords
does not change the yellow color. 10.1 amine values; fatty amines; total amine value

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