Designation: D 1411 – 99

AMERICAN SOCIETY FOR TESTING AND MATERIALS

100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods for

Water-Soluble Chlorides Present as Admixtures in Graded
Aggregate Road Mixes1
This standard is issued under the fixed designation D 1411; 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.

1. Scope * graded aggregate obtained from aggregate roads or aggregate

1.1 These test methods are applicable to the determination bases under paved roads is of interest to highway departments
of water-soluble calcium, magnesium, and sodium chlorides using calcium chloride or sodium chloride stabilization. The
used as admixtures in the preparation of graded aggregate road percentages of calcium chloride or sodium chloride obtained in
materials. these test methods are compared with the quantities added to
determine whether the road material and stabilizing agent were
NOTE 1—These test methods assume that the aggregate did not contain properly mixed, whether leaching of the stabilizing agent
significant amounts of the water-soluble chlorides in question before the
admixture was added. If significant amounts of these chlorides are known
occurred, etc.
or suspected to be present, the aggregate shall be tested for these
5. Purity of Reagents
constituents according to these test methods and the proper corrections
made. 5.1 Purity of Reagents—Reagent grade chemicals shall be
1.2 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.4 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: 5.2 Unless otherwise indicated, reference to water shall be
D 653 Terminology Relating to Soil, Rock, and Contained understood to mean distilled water or water of equal purity
Fluids2 conforming to Specification D 1193.
D 1193 Specification for Reagent Water3 6. Preparation of Samples
3. Terminology 6.1 Submit samples from the field to the laboratory in sealed
3.1 Except as follows in 3.2, all definitions are in accor- containers. For each individual sample, break up any large
dance with Terminology D 653. lumps in a mortar and quarter the sample. Accurately weigh
3.2 Definitions of Terms Specific to This Standard: approximately 300 g (dry weight) of a quartered sample and
3.2.1 admixture—a material other than water, aggregates, transfer it to a 1-L bottle. Add 479 mL of water, 20 mL of ferric
hydraulic cement, and fiber reinforcement used as an ingredi- ammonium sulfate (100 g/L) and 1 mL of ammonium hydrox-
ent and added immediately before or during the mixing of road ide (sp gr 0.90). Agitate in a shaker overnight or for 12 to 15
materials. h. Filter through fluted filter paper, discarding the first 50 mL
and retaining the remainder. Determine calcium, magnesium,
4. Significance and Use and chloride in the clear filtrate.
4.1 The percentage of calcium chloride, magnesium chlo- NOTE 2—The addition of ferric ammonium sulfate and ammonium
ride, and alkali chloride (calculated as sodium chloride) in hydroxide should give complete coagulation of most of the dispersible
materials and give clear filtrates.
1
These methods are under the jurisdiction of Committee D-18 on Soil and Rock
4
and are the direct responsibility of Subcommittee D18.15 on Stabilization with “Reagent Chemicals, American Chemical Society Specifications,” American
Admixtures. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Jan. 10, 1999. Published April 1999. Originally issued listed by the American Chemical Society, see Analar Standards for Laboratory
as D 1411 – 56 T. Last previous edition D 1411 – 98. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Annual Book of ASTM Standards, Vol 04.08. and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
3
Annual Book of ASTM Standards, Vol 11.01. MD.

*A Summary of Changes section appears at the end of this standard.

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 D 1411
TOTAL CHLORIDES 10.3 EDTA Standard Solution—Dissolve 3.792 g of diso-
dium dihydrogen ethylenediaminetetraacetate dihydrate in wa-
7. Reagents ter in a 1-L volumetric flask and dilute to volume with water.
7.1 Ammonium Thiocyanate, Standard Solution (0.1 N)— Standardize this solution by titrating 50.0 mL of the dilute
Dissolve 7.6 g of ammonium thiocyanate (NH4SCN) in water calcium chloride standard solution.
and dilute to 1 L. Standardize against the 0.1 N AgNO3 10.4 Hydroxylamine Hydrochloride, 10 % Solution—
solution. Dissolve 10 g of hydroxylamine hydrochloride (NH2OH·HCl)
7.2 Benzyl Alcohol, Chlorine-Free. in 90 mL of water.
7.3 Nitric Acid (sp gr 1.42)—Concentrated HNO3. 10.5 Potassium Cyanide.
7.4 Silver Nitrate, Standard Solution (0.1 N)—Dissolve 10.6 Sodium Hydroxide, Standard Solution (2 N)—
17.0 g of silver nitrate (AgNO3) in water and dilute to 1 L. This Dissolve 80 g of sodium hydroxide (NaOH) in 300 mL of
is a primary standard. water. Transfer to a 1-L volumetric flask and dilute to volume
7.5 Volhard Indicator Solution—Dissolve 10 g of ferric with water.
ammonium sulfate (FeNH4(SO4)2·12H2O) in 100 mL of water 10.7 Sugar.
and add 1 mL of HNO3. 11. Procedure
8. Procedure 11.1 Pipet a suitable aliquot of the solution of the sample
(see Section 6) 10.0 mL of the solution, or approximately 6 g
8.1 Acidify a suitable portion of the sample solution (see
of the original sample) into a 500-mL Erlenmeyer flask and
Section 6) (10-mL aliquot) with 3 to 5 mL of concentrated
dilute to about 200 mL.
HNO3, add a known volume of the 0.1 N AgNO3 solution that
11.2 Add 10 mL of the hydroxylamine hydrochloride solu-
is in excess of the amount required to precipitate the chloride,
tion, 1 g of sugar, and swirl to dissolve. Add 40 mL of the 2 N
and heat to boiling to coagulate silver chloride (AgCl). Cool to
NaOH solution and 0.1 g of potassium cyanide and about 0.2
room temperature, add 3 to 5 mL of benzyl alcohol, and shake
g of the indicator.
vigorously.
11.3 Titrate with standard EDTA solution until the indicator
8.2 Add Volhard indicator solution to the solution and titrate
changes from green to purple.
the excess AgNO3 with 0.1 N NH4SCN solution.
12. Calculation
9. Calculation
12.1 Calculate the percentage of calcium chloride (CaCl2)
9.1 Calculate the percentage of total chloride ion as follows: as follows:
@~aN 2 a8N8! 3 0.0355# Let F 5 g CaCl2/mL EDTA (2)
chloride, % bw 3 100 (1)
50.0 mL 3 0.000832 g CaCl2/mL
5 mL of EDTA from standardization
where:
a 5 millilitres of AgNO3 solution added, CaCl2, % 5 ~a 3 F 3 100!/bw (2)
a8 5 millilitres of NH4SCN solution required for the
titration, where:
N 5 normality of the AgNO3 solution, a 5 millilitres of EDTA solution required for the sample
N8 5 normality of NH4SCN solution, titration,
b 5 millilitres of solution in aliquot taken, divided by b 5 millilitres of solution in the aliquot taken, divided by
500, and 500, and
w 5 grams of sample used. w 5 grams of sample used.
MAGNESIUM CHLORIDE
CALCIUM CHLORIDE
13. Reagents
10. Reagents
13.1 Buffer Solution, Approximately pH 10—Dissolve 65.5
10.1 Calcein Modified Indicator.5 g of ammonium chloride in 300 mL of water. Add 570 mL of
10.2 Calcium Chloride, Standard Solution—Place 15.00 g ammonium hydroxide (NH4OH) (sp gr 0.90) and dilute to 1 L
of primary standard calcium carbonate (CaCO3) in 300 mL of with water.
water and slowly add concentrated hydrochloric acid (HCl), 13.2 Eriochrome Black T Indicator Solution—Dissolve 4.5
while stirring continuously. When the calcium carbonate is g of hydroxylamine hydrochloride (NH2OH·HCl) in 100 mL of
dissolved, cool and transfer to a 1-L volumetric flask. Dilute to methanol. Add 0.5 g of Eriochrome Black T and mix.
volume with water and mix thoroughly. Pipet a 25-mL aliquot
into a 500-mL volumetric flask and dilute to volume with water 14. Procedure
and mix thoroughly. One millilitre of the second dilution is 14.1 Pipet a suitable aliquot of the solution of the sample
equivalent to 0.000832 g of calcium chloride. (see Section 6) (10.0 mL of the solution, or approximately 6 g
of the original sample) into a 500-mL Erlenmeyer flask and
dilute to approximately 200 mL.
5
A satisfactory indicator is available from G. Frederich Smith Chemical Co., 14.2 Add 10 mL of 10 % hydroxylamine hydrochloride, 20
Columbus, OH. mL of buffer, 0.1 g potassium cyanide, 5 drops of indicator, and

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 D 1411
titrate with EDTA to a color change of red to blue. b 5 percent calcium chloride, and
c 5 percent magnesium chloride.
15. Calculation
PRECISION AND BIAS
15.1 Calculate the percentage of magnesium chloride
(MgCl2) as follows: 18. Precision and Bias
Let F 5 g of MgCl2/mL EDTA (3) 18.1 Precision—A limited interlaboratory round-robin test
50.0 mL 3 0.000832 g CaCl2/mL 3 0.858 program has been conducted for the purpose of establishing
5 mL of EDTA from standardization (3) precision and bias values. Total chlorides were determined by
MgCl2, % 5 @~a8 2 a! 3 F 3 100#/bw (3)
four laboratories with four samples. Table 1 describes the
standard deviation (1s) and the 95 % confidence interval (d2s)
where: for the total chloride contents tested. Two tests on similar
a8 5 millilitres of EDTA solution needed to titrate the specimens from the same sample should not differ by more
aliquot for calcium and magnesium. than the amounts indicated in the d2s columns.
a 5 millilitres of EDTA solution needed to titrate the 18.2 The bias for this round-robin test was on the order of
aliquot for calcium, minus 35 %. That is, the average results in the four tentative
b 5 millilitres in the aliquot of the original sample solu- tests were approximately 35 % lower than the actual values
tion, divided by 500, and which should have been obtained. A more extensive interlabo-
w 5 grams of sample used. ratory round-robin test series has been proposed to resolve the
question of accuracy.6
ALKALI CHLORIDE
19. Keywords
16. Procedure 19.1 admixture; chloride content; soil-stabilization
16.1 Alkali chlorides are calculated from the difference of
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the total chloride and calcium and magnesium determinations. Details of the precision and bias analysis are on file with ASTM. Request RR:
D–18–1001.
17. Calculation
TABLE 1 Estimates of Precision
17.1 Calculate the percentage of alkali chlorides as follows:
Single operator Multi-laboratory
Percent alkali chlorides as NaCl (4)
Material 1s d2s 1s d2s
5 ~a 3 1.648! 2 ~b 3 1.053! 2 ~c 3 1.227! (4)
2 % NaCl 0.0082 0.0232 0.0087 0.0246
2.5 % CaCl2 0.0137 0.0387 0.0138 0.0390
where: 3 % NaCl 0.0115 0.0325 0.0120 0.0339
a 5 percent total chlorides, 3.5 % CaCl2 0.0128 0.0362 0.0172 0.0486

SUMMARY OF CHANGES

This section identifies the location of changes to this test method since the last edition.

(1) The word “admix” was replaced with “admixture” in the (4) Section 3, Terminology, was added to incorporate a new
title and paragraph 1.1 because, according to the dictionary, the definition. Subsequent sections were renumbered.
word “admix” is grammatically incorrect in these circum- (5) A new definition of “admixture” was added to Section 3,
stances. Terminology, because the one found in Terminology D 653 is
(2) Paragraph 1.2 (safety caveat) was added in accordance with written for grouts.
the Form and Style Manual (Blue Book).
(6) Summary of Changes was added.
(3) Terminology D 653 was added to Section 2, Referenced
Documents.

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