An American National Standard

Designation: D1067 – 11

Standard Test Methods for

Acidity or Alkalinity of Water1
This standard is issued under the fixed designation D1067; 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 Department of Defense.

1. Scope* applications. When titrating to a selected end point dictated by

1.1 These test methods2 cover the determination of acidity practical considerations, (1) only a part of the actual neutral-
or alkalinity of all types of water. Three test methods are given izing capacity of the water may be measured, or (2) this
as follows: capacity may actually be exceeded in arriving at optimum
Sections
acidity or alkalinity conditions.
Test Method A (Electrometric Titration) 7 to 15 1.4 A scope section is provided in each test method as a
Test Method B (Electrometric or Color-Change Titration) 16 to 24 guide. It is the responsibility of the analyst to determine the
Test Method C (Color-Change Titration After Hydrogen 25 to 33
Peroxide Oxidation and Boiling)
acceptability of these test methods for each matrix.
1.5 Former Test Methods C (Color-Comparison Titration)
1.2 In all of these test methods the hydrogen or hydroxyl and D (Color-Change Titration After Boiling) were discontin-
ions present in water by virtue of the dissociation or hydrolysis ued. Refer to Appendix X4 for historical information.
of its solutes, or both, are neutralized by titration with standard 1.6 The values stated in SI units are to be regarded as
alkali (acidity) or acid (alkalinity). Of the three procedures, standard. No other units of measurement are included in this
Test Method A is the most precise and accurate. It is used to standard.
develop an electrometric titration curve (sometimes referred to 1.7 This standard does not purport to address all of the
as a pH curve), which defines the acidity or alkalinity of the safety concerns, if any, associated with its use. It is the
sample and indicates inflection points and buffering capacity, if responsibility of the user of this standard to establish appro-
any. In addition, the acidity or alkalinity can be determined priate safety and health practices and determine the applica-
with respect to any pH of particular interest. The other two bility of regulatory limitations prior to use.
methods are used to determine acidity or alkalinity relative to
a predesignated end point based on the change in color of an 2. Referenced Documents
internal indicator or the equivalent end point measured by a pH 2.1 ASTM Standards:3
meter. They are suitable for routine control purposes. D596 Guide for Reporting Results of Analysis of Water
1.3 When titrating to a specific end point, the choice of end D1066 Practice for Sampling Steam
point will require a careful analysis of the titration curve, the D1129 Terminology Relating to Water
effects of any anticipated changes in composition on the D1193 Specification for Reagent Water
titration curve, knowledge of the intended uses or disposition D1293 Test Methods for pH of Water
of the water, and a knowledge of the characteristics of the D2777 Practice for Determination of Precision and Bias of
process controls involved. While inflection points (rapid Applicable Test Methods of Committee D19 on Water
changes in pH) are usually preferred for accurate analysis of D3370 Practices for Sampling Water from Closed Conduits
sample composition and obtaining the best precision, the use of D5847 Practice for Writing Quality Control Specifications
an inflection point for process control may result in significant for Standard Test Methods for Water Analysis
errors in chemical treatment or process control in some E200 Practice for Preparation, Standardization, and Storage
of Standard and Reagent Solutions for Chemical Analysis
1
These test methods are under the jurisdiction of ASTM Committee D19 on 3. Terminology
Water and are the responsibility of Subcommittee D19.05 on Inorganic Constituents
in Water. 3.1 Definitions—The terms in these test methods are defined
Current edition approved April 1, 2011. Published April 2011. Originally in accordance with Terminology D1129.
approved in 1949. Last previous edition approved in 2006 as D1067 – 06. DOI:
10.1520/D1067-11.
2 3
The basic procedures used in these test methods have appeared widespread in For referenced ASTM standards, visit the ASTM website, www.astm.org, or
the technical literature for many years. Only the particular adaptation of the contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
electrometric titration appearing as the Referee Method is believed to be largely the Standards volume information, refer to the standard’s Document Summary page on
work of Committee D19. the ASTM website.

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

Copyright. (C) ASTM International. 100 Barr Harbour Drive, P.O. Box C-700, West Conshohocken PA. United States

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 D1067 – 11
3.1.1 Certain uses of terminology exist in the water treat- acidity or alkalinity of the water or that relative to a particular
ment industry which may differ from these definitions. A pH is determined from the curve.
discussion of terms is presented in Appendix X1.
8. Summary of Test Method
4. Significance and Use 8.1 To develop a titration curve that will properly identify
4.1 Acidity and alkalinity measurements are used to assist in the inflection points, standard acid or alkali is added to the
establishing levels of chemical treatment to control scale, sample in small increments and a pH reading is taken after each
corrosion, and other adverse chemical equilibria. addition. The cumulative volume of solution added is plotted
4.2 Levels of acidity or alkalinity are critical in establishing against the observed pH values. All pH measurements are
solubilities of some metals, toxicity of some metals, and the made electrometrically.
buffering capacity of some waters.
9. Interferences
5. Purity of Reagents 9.1 Although oily matter, soaps, suspended solids, and other
5.1 Reagent grade chemicals shall be used in all tests. waste materials may interfere with the pH measurement, these
Unless otherwise indicated, it is intended that all reagents shall materials may not be removed to increase precision, because
conform to the specifications of the Committee on Analytical some are an important component of the acid- or alkali-
Reagents of the American Chemical Society, where such consuming property of the sample. Similarly, the development
specifications are available.4 Other grades may be used, pro- of a precipitate during titration may make the glass electrode
vided it is first ascertained that the reagent is of sufficiently sluggish and cause high results.
high purity to permit its use without lessening the accuracy of
10. Apparatus
the determination.
5.2 Unless otherwise indicated, references to water shall be 10.1 Electrometric pH Measurement Apparatus, conform-
understood to mean reagent water conforming to Specification ing to the requirements given in Test Methods D1293.
D1193, Type I. In addition, reagent water for this test shall be
11. Reagents 4
free of carbon dioxide (CO2) and shall have a pH between 6.2
and 7.2 at 25°C. Other reagent water types may be used 11.1 Hydrochloric Acid, Standard (0.02 N) (see Note 1)—
provided it is first ascertained that the water is of sufficiently Prepare and standardize as directed in Practice E200, except
high purity to permit its use without adversely affecting the that the titration shall be made electrometrically. The inflection
precision and bias of the test method. Type III water was point corresponding to the complete titration of carbonic acid
specified at the time of round robin testing of this test method. salts will be very close to pH 3.9.
A procedure for the preparation of carbon dioxide-free water is NOTE 1—Sulfuric acid of similar normality may be used instead of
given in Practice E200. hydrochloric acid. Prepare and standardize in like manner.
11.2 Sodium Hydroxide, Standard (0.02 N)—Prepare and
6. Sampling
standardize as directed in Practice E200, except that the
6.1 Collect the sample in accordance with Practice D1066 titration shall be made electrometrically. The inflection point
and Practices D3370 as applicable. corresponding to the complete titration of the phthalic acid salt
6.2 The time interval between sampling and analysis shall will be very close to pH 8.6.
be as short as practically possible in all cases. It is mandatory
that analyses by Test Method A be carried out the same day the 12. Procedure
samples are taken; essentially immediate analysis is desirable 12.1 Mount the glass and reference electrodes in two of the
for those waste waters containing hydrolyzable salts that holes of a clean, threehole rubber stopper chosen to fit a
contain cations in several oxidation states. 300-mL, tall-form Berzelius beaker without spout, or equiva-
lent apparatus. Alternatively, a combination pH electrode can
TEST METHOD A—ELECTROMETRIC TITRATION be used that has both a glass and a reference electrode in an
integral unit. Place the electrodes in the beaker and standardize
7. Scope the pH meter, using a reference buffer having a pH approxi-
7.1 This test method is applicable to the determination of mating that expected for the sample (see Test Methods D1293).
acidity or alkalinity of all waters that are free of constituents Rinse the electrodes, first with reagent water, then with a
that interfere with electrometric pH measurements. It is used portion of the sample. Following the final rinse, drain the
for the development of a titration curve that will define beaker and electrodes completely.
inflection points and indicate buffering capacity, if any. The 12.2 Pipette 100 mL of the sample, adjusted, if necessary, to
room temperature, into the beaker through the third hole in the
stopper. Hold the tip of the pipette near the bottom of the
4
Reagent Chemicals, American Chemical Society Specifications, American beaker while discharging the sample.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not 12.3 Measure the pH of the sample in accordance with Test
listed by the American Chemical Society, see Analar Standards for Laboratory
Methods D1293.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopoeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 12.4 Add either 0.02 N acid or alkali solution, as indicated,
MD. in increments of 0.5 mL or less (see Note 2). After each

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 D1067 – 11
addition, mix the solution thoroughly. Determine the pH when TABLE 1 Determination of Precision and Bias for Acidity and
the mixture has reached equilibrium as indicated by a constant Alkalinity by Electrometric Titration (Test Method A)
reading (see Note 3). Mechanical stirring, preferably of the Amount Amount
Bias,
Added, Found, St So
magnetic type, is required for this operation; mixing by means meq/L meq/L
%
of a gas stream is not permitted. Continue the titration until the
Acidity
necessary data for the titration curve have been obtained. 48.30 48.76 1.25 0.44 +0.94
23.00 22.61 0.68 0.27 −1.67
NOTE 2—If the sample requires appreciably more than 25 mL of 17.10 16.51 0.71 0.26 −3.47
standard solution for its titration, use a smaller aliquot, or a 0.1 N solution, Alkalinity
prepared and standardized in the same manner (see Practice E200). 4.90 5.00 0.39 0.12 +2.12
NOTE 3—An electrometric titration curve is smooth, with the pH 2.46 2.45 0.14 0.06 −0.00
changing progressively in a single direction, if equilibrium is achieved 0.51 0.56 0.15 0.05 +10.59
after each incremental addition of titrant, and may contain one or more
inflection points. Ragged or irregular curves may indicate that equilibrium
was not attained before adding succeeding increments. The time required
will vary with different waters as the reaction rate constants of different TEST METHOD B—ELECTROMETRIC OR COLOR-
chemical equilibria vary. In some instances the reaction time may be an
CHANGE TITRATION
interval of a few seconds while other slower, more complex reactions may
require much longer intervals. It is important, therefore, that the period be
sufficient to allow for any significant pH changes, yet consistent with good 16. Scope
laboratory practices.
16.1 This test method covers the rapid, routine control
12.5 To develop a titration curve, plot the cumulative measurement of acidity or alkalinity to predesignated end
milliliters of standard solution added to the sample aliquot points of waters that contain no materials that buffer at the end
against the observed pH values. The acidity or alkalinity point or other materials that interfere with the titration by
relative to a particular pH may be determined from the curve. reasons that may include color or precipitation.
13. Calculation 17. Summary of Test Method
13.1 Calculate the acidity or alkalinity, in milliequivalents
17.1 The sample is titrated with standard acid or alkali to a
per litre, using Eq 1:
designated pH, the end point being determined electrometri-
Acidity ~or alkalinity!, meq/L ~epm! 5 AN/B 3 1000 (1) cally or by the color change of an internal indicator.
where:
1000 = 1000 mL / liter 18. Interferences
A = standard acid or alkali required for the titration, mL, 18.1 Natural color or the formation of a precipitate while
N = normality of the standard solution, and titrating the sample may mask the color change of an internal
B = sample titrated, mL. indicator. Suspended solids may interfere in electrometric
titrations by making the glass electrode sluggish. Waste mate-
14. Report
rials present in some waters may interfere chemically with
14.1 Report the results of titrations to specific end points as color titrations by destroying the indicator. Variable results
follows: “The acidity (or alkalinity) to pH at °C = meq/L may be experienced with waters containing oxidizing or
(epm).” reducing substances, depending on the equilibrium conditions
14.2 Appropriate factors for converting milliequivalents per and the manner in which the sample is handled.
litre (epm) to other units are given in Guide D596.
19. Apparatus
15. Precision and Bias 5
15.1 The precision and bias data presented in Table 1 for 19.1 Electrometric pH Measurement Apparatus—See 10.1.
this test method meet the requirements of Practice D2777.
15.2 The collaborative test of this test method was per- 20. Reagents
formed in reagent waters by six laboratories using one operator 20.1 Bromcresol Green Indicator Solution (l g/L)—Dissolve
each, using three levels of concentration for both the acidity 0.1 g of bromcresol green in 2.9 mL of 0.02 N sodium
and alkalinity. hydroxide (NaOH) solution. Dilute to 100 mL with water.
15.3 Precision and bias for this test method conforms to 20.2 Hydrochloric Acid, Standard (0.02 N) (Note 1)—See
Practice D2777–77, which was in place at the time of collab- 11.1, except that the acid may be standardized by colorimetric
orative testing. Under the allowances made in 1.4 of Practice titration as directed in Practice E200 when an indicator is used
D2777–08, these precision and bias data do meet existing for sample titration.
requirements for interlaboratory studies of Committee D19 test
methods. 20.3 Methyl Orange Indicator Solution (0.5 g/L)—Dissolve
0.05 g of methyl orange in water and dilute to 100 mL.
20.4 Methyl Purple Indicator Solution (l g/L)—Dissolve
5
Supporting data have been filed at ASTM International Headquarters and may 0.45 g of dimethyl-aminoazobenzene-O-carboxylic acid, so-
be obtained by requesting Research Report RR:D19-1149. dium salt, in approximately 300 mL of water. To this solution

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 D1067 – 11
add 0.55 g of a water-soluble blue dye-stuff, Color Index No. TABLE 2 Determination of Precision and Bias for Acidity and
714,6,7 and dissolve. Dilute to 1 L with water. Alkalinity by Electrometric or Color-Change Titration
(Test Method B)
20.5 Methyl Red Indicator Solution (1 g/L)—Dissolve 0.1 g
Amount Amount
of water-soluble methyl red in water and dilute to 100 mL. Added, Found, St So
Bias,
20.6 Phenolphthalein Indicator Solution (5 g/L)—Dissolve %
meq/L meq/L
0.5 g of phenolphthalein in 50 mL of ethyl alcohol (95 %) and Acidity
dilute to 100 mL with water. 48.30 49.06 0.802 0.589 + 1.57
23.00 22.83 0.610 0.455 −0.74
NOTE 4—Specially denatured ethyl alcohol conforming to Formula No. 17.10 16.84 0.334 0.146 −1.52
3A or 30 of the U. S. Bureau of Internal Revenue may be substituted for Alkalinity
ethyl alcohol (95 %). 4.90 4.88 0.156 0.034 −0.41
1.92 1.80 0.080 0.014 −6.25
NOTE 5—Indicators are available commercially in prepared form.
0.51 0.50 0.044 0.024 −1.96
20.7 Sodium Hydroxide, Standard (0.02 N)—See 11.2, ex-
cept that the alkali may be standardized by colorimetric
titration as directed in Practice E200 when an indicator is used
for sample titration. where:
1000 = 1000 mL / liter
A = standard acid or alkali required for the titration, mL,
21. Procedure N = normality of the standard solution, and
21.1 Depending on the method of titration to be used, B = sample titrated, mL.
pipette 100 mL of the sample, adjusted, if necessary, to room
temperature, into a 300-mL, tall-form beaker or a 250-mL, 23. Report
narrow-mouth Erlenmeyer flask. Hold the tip of the pipette 23.1 Report the results of titration as follows: “The acidity
near the bottom of the container while discharging the sample. (or alkalinity) to at °C = meq/L (epm),” indicating the pH and
21.2 Titrate the aliquot electrometrically to the pH corre- the temperature at which it was determined, or the name of the
sponding to the desired end point (see Note 6). When using an indicator used, for example, “The acidity to methyl orange at
indicator, add 0.2 mL (see Note 7) and titrate with 0.02 N acid °C = meq/L (epm).”
(for alkalinity) or 0.02 N NaOH solution (for acidity) until a
persistent color change is noted (see Note 8). Add the standard 24. Precision and Bias 5
solution in small increments, swirling the flask vigorously after 24.1 The precision and bias data presented in Table 2 for
each addition. As the end point is approached, a momentary this test method meet the requirements of Practice D2777.
change in color will be noted in that portion of the sample with 24.2 The collaborative test of this test method was per-
which the reagent first mixes. From that point on, make formed in reagent waters by six laboratories using one operator
dropwise additions. each, using three levels of concentration for both the acidity
NOTE 6—The choice of end point will have been made to provide and alkalinity.
optimum data for the intended use or disposition of the water. When an 24.3 Precision and bias for this test method conforms to
indicator is used, those listed in 20.1 and 20.3 through 20.6 are used most Practice D2777–77, which was in place at the time of collab-
frequently; others may be employed if it is to the user’s advantage. Color orative testing. Under the allowances made in 1.4 of Practice
change and endpoint data for indicators listed herein are presented in D2777–08, these precision and bias data do meet existing
Appendix X2 and Table X2.1.
NOTE 7—After some practice, slightly more or less indicator may be
requirements for interlaboratory studies of Committtee D19
preferred. The analyst must use the same quantity of phenolphthalein at all test methods.
times, however, because at a given pH, the intensity of one-color
indicators depends on the quantity. TEST METHOD C—COLOR-CHANGE TITRATION
NOTE 8—If the sample requires appreciably more than 25 mL of 0.02 N AFTER HYDROGEN PEROXIDE OXIDATION AND
solution for its titration, use a smaller aliquot, or a 0.1 N reagent prepared BOILING
and standardized in the same manner (see Practice E200).
25. Scope
22. Calculation
25.1 This test method is intended specifically for mine
22.1 Calculate the acidity or alkalinity, in milliequivalents drainage, surface streams receiving mine drainage, industrial
per liter, using Eq 2: waste waters containing waste acids and their salts, and similar
Acidity ~or alkalinity!, meq/L ~epm! 5 ~AN/B! 3 1000 (2) waters bearing substantial amounts of ferrous iron or other
polyvalent cations in a reduced state.
25.2 Because the oxidation and hydrolysis of ferrous iron
6
generate acidity, a reliable measure of acidity or alkalinity is
Refers to compounds, bearing such number, as described in “Color Index,”
Society of Dyers and Colourists, Yorkshire, England (1924). obtained only when complete oxidation is achieved and hydro-
7
The sole source of supply of the dye (Calcocid Blue AX Double) known to the lysis to ferric salts is completed (see Appendix X3). In many
committee at this time is American Cyanamid Company, One Cyanamid Plaza, instances, the concentration of ferrous iron is such that a 2-min
Wayne, NJ 07470. If you are aware of alternative suppliers, please provide this
information to ASTM International Headquarters. Your comments will receive
boiling period is not sufficient to assure complete oxidation. In
careful consideration at a meeting of the responsible technical committee,1 which this test method, hydrogen peroxide is added prior to boiling to
you may attend. accelerate the chemical reactions needed for equilibrium.

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 D1067 – 11
25.3 This test method may be used to determine approxi- TABLE 3 Determination of Precision and Bias for Acidity by
mate alkali requirements for neutralization and to assure Color-Change Titration After Hydrogen Peroxide Oxidation and
Boiling (Test Method C)
comparability of results when both alkaline and acid flows are
Amount Amount
under consideration in mine drainage treatment. Added, Found, St So
Bias,
%
meq/L meq/L
26. Summary of Test Method
Acidity
26.1 The pH of the sample is determined. Standard acid is 48.30 49.06 1.28 0.43 +1.57
added as needed to lower the pH to 4.0 or less. Hydrogen 23.00 23.00 0.46 0.37 0.00
0.07 0.15 0.12 0.69 +106.0
peroxide (H2O2) is added, the solution boiled, and finally either
titrated while hot to the phenolphthalein end point, or cooled
and titrated electrometrically with standard alkali to pH = 8.2, 31.1.2 Where sulfuric acid is added:
the desired end point.
Acidity ~boiled and oxidized!, meq/L ~epm! 5 [~BNb 2 ANa!/S]
27. Interferences 3 1000 ~see Note10! (4)

27.1 Natural color or the formation of a colored precipitate where:

during boiling may mask the color change of the phenolphtha- 1000 = 1000 mL / liter
lein end point, requiring a pH meter for the titration. Suspended A = H2SO4 added to sample, mL,
solids may cause sluggishness in electrometric titrations; B = NaOH solution required for titration of sample, mL,
however, compensation is made by a 15-s pause between alkali Na = normality of the H2SO4,
additions or by dropwise addition of titrant when the desig- Nb = normality of the NaOH solution, and
nated pH is approached. S = sample used, mL.
27.2 The standard acid added prior to boiling neutralizes NOTE 10—Minus acidity represents excess alkalinity contributed by
volatile components, for example, bicarbonates which contrib- constituents such as bicarbonates.
ute to the alkalinity and, hence, minimizes this source of error.
32. Report
28. Apparatus 32.1 Report the results of titrations as follows: “The acidity
28.1 Electrometric pH Measurement Apparatus—See 10.1. (boiled and oxidized) to pH (or phenolphthalein) = meq/L
(epm).”
29. Reagents
29.1 Hydrogen Peroxide (H2O2, 30 % Solution). 33. Precision and Bias 5
29.2 Phenolphthalein Indicator Solution (5 g/L)—See 20.6. 33.1 The precision and bias data presented in Table 3 for
29.3 Sodium Hydroxide, Standard (0.02 N)—Prepare and this test method meet the requirements of Practice D2777.
standardize as directed in Practice E200. 33.2 The collaborative test of this test method was per-
29.4 Sulfuric Acid, Standard (0.02 N)—Prepare and stan- formed in reagent waters by six laboratories using one operator
dardize as directed in Practice E200. each, using three levels of concentration for both the acidity
and alkalinity.
NOTE 9—Hydrochloric acid of similar normality may be used instead of
33.3 Precision and bias for this test method conforms to
sulfuric acid. Prepare and standardize in like manner.
Practice D2777–77, which was in place at the time of collab-
30. Procedure orative testing. Under the allowances made in 1.4 of Practice
30.1 Pipette 50 mL of the sample into a 250-mL beaker. D2777–08, these precision and bias data do meet existing
30.2 Measure the pH of the sample (see Test Methods requirements for interlaboratory studies of D19 test methods.
D1293). If the pH is above 4.0, add 5-mL increments of 34. Quality Control
standard H2SO4 to lower the pH to 4.0 or less (see Note 9).
34.1 In order to be certain that analytical values obtained
30.3 Add only 5 drops of H2O2.
using these test methods are valid and accurate within the
30.4 Heat the sample to boiling and continue to boil for 2 to
confidence limits of the test, the following QC procedures must
4 min.
be followed when analyzing acidity or alkalinity.
30.5 If the sample is discolored, cool to room temperature
34.1.1 Calibration and Calibration Verification:
and titrate electrometrically with standard NaOH solution to
34.1.1.1 Calibrate according to Test Methods D1293.
pH = 8.2, corresponding to the desired end point. If the sample
34.1.1.2 Verify instrument calibration after standardization
is colorless, titrate to the phenolphthalein color change while
by analyzing a pH solution.
hot.
34.1.1.3 If calibration cannot be verified, recalibrate the
31. Calculation instrument.
34.1.2 Initial Demonstration of Laboratory Capability:
31.1 Calculate the acidity in milliequivalents per liter using
34.1.2.1 If a laboratory has not performed the test before, or
Eq 3 or Eq 4:
if there has been a major change in the measurement system,
31.1.1 Where no sulfuric acid is added:
for example, new analyst, new instrument, etc., a precision and
bias study must be performed to demonstrate laboratory
Acidity ~boiled and oxidized!, meq/L ~epm! 5 ~BNb/S! 3 1000 (3) capability.

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 D1067 – 11
34.1.2.2 Analyze seven replicates of a standard solution 34.1.3.2 If the result is not within the precision limit,
prepared from an Independent Reference Material containing a analysis of samples is halted until the problem is corrected, and
mid-range concentration acidity or alkalinity. The matrix and either all the samples in the batch must be reanalyzed, or the
chemistry of the solution should be equivalent to the solution results must be qualified with an indication that they do not fall
used in the collaborative study. Each replicate must be taken within the performance criteria of the test method.
through the complete analytical test method including any 34.1.4 Duplicate:
sample pretreatment steps. 34.1.4.1 To check the precision of sample analyses, analyze
a sample in duplicate with each batch.
34.1.2.3 Calculate the mean and standard deviation of the
34.1.4.2 Calculate the standard deviation of the duplicate
seven values and compare to the bias in Table 1, Table 2, or values and compare to the precision in the collaborative study
Table 3 (depending on the method used). This study should be using an F test. Refer to 6.4.4 of Practice D5847 for informa-
repeated until the recoveries are statistically equivalent to or tion on applying the F test.
better than those in Table 1, Table 2, or Table 3. If a 34.1.4.3 If the result exceeds the precision limit, the batch
concentration other than the recommended concentration is must be reanalyzed or the results must be qualified with an
used, refer to Practice D5847 for information on applying the indication that they do not fall within the performance criteria
F test and t test in evaluating the acceptability of the mean and of the test method.
standard deviation. 34.1.5 Independent Reference Material (IRM):
34.1.3 Laboratory Control Sample (LCS): 34.1.5.1 In order to verify the quantitative value produced
34.1.3.1 To ensure that the test method is in control, analyze by the test method, analyze an Independent Reference Material
(IRM) submitted as a regular sample (if practical) to the
a LCS containing a mid-range concentration of acidity or
laboratory at least once per quarter. The concentration of the
alkalinity with each batch or 10 samples. If large numbers of
IRM should be in the concentration mid-range for the method
samples are analyzed in the bath, analyze the LCS after every
chose. The value obtained must fall within the control limits
10 samples. The LCS must be taken through all of the steps of established by the laboratory.
the analytical method, including sample pretreatment. The
result obtained for the LCS shall fall within 615 % of the 35. Keywords
known concentration. 35.1 acidity; alkalinity; titrations; water

APPENDIXES

(Nonmandatory Information)

X1. DISCUSSION OF TERMS

X1.1 The terms, acidity and alkalinity, as used in water waste waters, are common causes of acidity. Acidity determi-
analysis may not be in accord with generally accepted termi- nations on waters containing ferrous iron are further compli-
nology with a neutral point at pH 7. In water analysis, a pH of cated by air oxidation of ferrous to the ferric state and
about 4.5 is frequently the end point for titration of alkalinity subsequent hydrolysis to produce additional acidity.
and a pH of about 8.2 for acidity.
X1.4 Since some water samples change on storage, analy-
X1.2 In addition to free hydroxide, alkalinity may be ses must be made without delay or results may be of little
produced by anions that tend to hydrolyze; these include value. Interpretation of acidity and alkalinity data should be
carbonate, bicarbonate, silicate, phosphate, borate, arsenate, made cautiously. For a more thorough understanding of the
aluminate, possibly fluoride, and certain organic anions in subject, it is recommended that the analyst review the litera-
waste waters. All the effects due to these anions are lumped ture8,9,10. Then, the analyst may be able to develop an
together in an alkalinity analysis. interpretation of his data better suited to his particular needs.
X1.3 The factors causing acidity in water are also complex.
Acidic materials encountered in water analysis include, in 8
Hem, J. D., “Study and Interpretation of The Chemical Characteristics of
addition to free organic and mineral acids, uncombined dis- Natural Water,” Geological Survey Water-Supply Paper 1473, 1959, pp. 92–100.
9
Rainwater, F. H., and Thatcher, L. L., “Methods for Collection and Analysis of
solved gases, and acids formed on hydrolysis of salts of weak
Water Samples,” Geological Survey Water-Supply Paper 1454, 1960, pp. 87–95.
bases and strong acids. Hydrolyzable salts of aluminum and 10
Sawyer, C. N., Chemistry for Sanitary Engineers, McGraw-Hill Book Co.,
ferric and ferrous iron in mine drainage and certain industrial Inc., New York, NY, 1960, pp. 211–227.

Copyright by ASTM Int'l (all rights reserved); 6

 D1067 – 11

X2. INTERNAL ACID-BASE INDICATORS

X2.1 Table X2.1 is provided as a guide in the selection of

TABLE X2.1 pH End Points Equivalent to Color Change of Indicators

Range End Point
Indicator
pH Color pH Color
Phenolphthalein 8.0 to 10 colorless-red 8.2 pink
Methyl orange 3.2 to 4.4 pink-yellow 4.2 pink-orange
Methyl purple A 4.8 to 5.5 purple-green 4.9 gray-purple
Methyl red 4.2 to 6.2 pink-yellow 5.5 orange
Bromcresol green 4.0 to 5.4 yellow-blue 4.5 green
Bromphenol blue 3.0 to 4.6 yellow-blue 3.7 green
A
Available as a prepared reagent from most chemical supply houses.

a titration indicator for determinations of acidity and alkalinity.

X3. USES OF THE HYDROGEN PEROXIDE TEST METHOD

X3.1 The hydrogen peroxide test method is particularly decreases the pH, resulting in a fading end point.
suitable for assessing the acidity of mine drainage waters that
are discharged into public streams. Under such conditions, all X3.3 Both problems can be avoided by oxidizing the
ferrous iron is rapidly oxidized to the ferric state, resulting in ferrous ion with hydrogen peroxide prior to titration:
the precipitation of Fe(OH)3:
2 Fe 1 2 1 H2O2 1 2H 1 1 → 2 Fe 1 3 1 2H2O (X3.2)
2 Fe 1 2 1 1 / 2 O2 1 4 OH 2 1 1 H2O → 2 Fe~OH!3 (X3.1)
During the subsequent titration, the ferric ion is precipitated
X3.2 The presence of ferrous ion in waters creates a as ferric hydroxide:
twofold problem. First, the solubility of ferrous ion at a pH of
Fe 1 3 1 3 OH 2 1 → Fe~OH!3 (X3.3)
8.2 (phenolphthalein end point) is appreciable and the full
acidity potential of the water cannot be assessed by direct Note that in Eq X3.2 and Eq X3.3, the net effect is that two
titration to this end point. Second, at a pH of 8.2, soluble hydroxyl ions are consumed for each ferrous ion originally
ferrous iron is rapidly oxidized by atmospheric oxygen. Sub- present, although the end product in each case is ferric
sequent hydrolysis of the resultant ferric ion immediately hydroxide.

X4. RATIONALE FOR DISCONTINUATION OF TEST METHODS

X4.1 Color-Comparison Titration: X4.2 Color-Change Titration After Boiling:

X4.1.1 This test method was discontinued in 1988. The test X4.2.1 This test method was discontinued in 1988. The test
method may be found in its entirety in the 1988 Annual Book method may be found in its entirety in the 1988 Annual Book
of ASTM Standards, Vol 11.01. of ASTM Standards, Vol 11.01.
X4.1.2 This test method is applicable to routine control used X4.2.2 This test method is applicable to routine control
in determining the acidity or alkalinity to a particular end point measurement of acidity or alkalinity of waters containing
of waters containing no materials that buffer at the end point or concentrations of slowly hydrolyzable materials sufficient to
interfere with the titration due to color or precipitation, or other significantly delay attainment of equilibrium conditions at a
reasons. titration end point. It is particularly applicable to mine drain-
X4.1.3 The sample is titrated with standard acid or alkali to age, industrial waste waters carrying waste acids, and similar
a predesignated pH, the end point being determined by waters. Volatile components contributing to the acidity or
comparison of the color developed by an added indicator with alkalinity of the water may be lost during sample pretreatment.
the color of a standard buffer solution containing the same X4.2.3 The sample aliquot (acidified if alkaline) is boiled to
added indicator. accelerate chemical reactions for attaining equilibrium condi-
X4.1.4 This test method was discontinued because there tions, cooled, and titrated with standard acid or alkali to a
were insufficient laboratories interested in participating in predesignated end point. Titration is carried out by means of an
another collaborative study to obtain the necessary precision internal indicator using the color-change procedure described
and bias as required by Practice D2777. in Test Method B (Electrometric or Color-Change Titration).

Copyright by ASTM Int'l (all rights reserved); 7

 D1067 – 11
X4.2.4 This test method was discontinued because there
were insufficient laboratories interested in participating in
another collaborative study to obtain the necessary precision
and bias as required by Practice D2777.

SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue
(D1067 – 06) that may impact the use of this standard.

(1) Clarified 13.1, 22.1, and 31.1.2. (2) Modified 34.1.2.2.

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