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 U.S. Department of Defense.

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

2
1.1 These test methods 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
acidity or alkalinity conditions.
Sections
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.
1.2 In all of these test methods the hydrogen or hydroxyl 1.5 Former Test Methods C (Color-Comparison Titration)
ions present in water by virtue of the dissociation or hydrolysis and D (Color-Change Titration After Boiling) were discontin-
of its solutes, or both, are neutralized by titration with standard ued. Refer to Appendix X4 for historical information.
alkali (acidity) or acid (alkalinity). Of the three procedures, 1.6 The values stated in SI units are to be regarded as
Test Method A is the most precise and accurate. It is used to standard. No other units of measurement are included in this
develop an electrometric titration curve (sometimes referred to standard.
as a pH curve), which defines the acidity or alkalinity of the 1.7 This standard does not purport to address all of the
sample and indicates inflection points and buffering capacity, if safety concerns, if any, associated with its use. It is the
any. In addition, the acidity or alkalinity can be determined responsibility of the user of this standard to establish appro-
with respect to any pH of particular interest. The other two priate safety and health practices and determine the applica-
methods are used to determine acidity or alkalinity relative to bility of regulatory limitations prior to use.
a predesignated end point based on the change in color of an
internal indicator or the equivalent end point measured by a pH 2. Referenced Documents
meter. They are suitable for routine control purposes. 2.1 ASTM Standards:3
1.3 When titrating to a specific end point, the choice of end D596 Guide for Reporting Results of Analysis of Water
point will require a careful analysis of the titration curve, the D1066 Practice for Sampling Steam
effects of any anticipated changes in composition on the D1129 Terminology Relating to Water
titration curve, knowledge of the intended uses or disposition D1193 Specification for Reagent Water
of the water, and a knowledge of the characteristics of the D1293 Test Methods for pH of Water
process controls involved. While inflection points (rapid D2777 Practice for Determination of Precision and Bias of
changes in pH) are usually preferred for accurate analysis of Applicable Test Methods of Committee D19 on Water
sample composition and obtaining the best precision, the use of D3370 Practices for Sampling Water from Closed Conduits
an inflection point for process control may result in significant D5847 Practice for Writing Quality Control Specifications
errors in chemical treatment or process control in some for Standard Test Methods for Water Analysis
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
Water and are the responsibility of Subcommittee D19.05 on Inorganic Constituents
3. Terminology
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 © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. 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
the determination. 10. Apparatus
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
free of carbon dioxide (CO2) and shall have a pH between 6.2 11. Reagents4
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
given in Practice E200. NOTE 1—Sulfuric acid of similar normality may be used instead of
hydrochloric acid. Prepare and standardize in like manner.
6. Sampling 11.2 Sodium Hydroxide, Standard (0.02 N)—Prepare and
6.1 Collect the sample in accordance with Practice D1066 standardize as directed in Practice E200, except that the
and Practices D3370 as applicable. titration shall be made electrometrically. The inflection point
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
for those waste waters containing hydrolyzable salts that 12.1 Mount the glass and reference electrodes in two of the
contain cations in several oxidation states. holes of a clean, threehole rubber stopper chosen to fit a
300-mL, tall-form Berzelius beaker without spout, or equiva-
TEST METHOD A—ELECTROMETRIC TITRATION lent apparatus. Alternatively, a combination pH electrode can
be used that has both a glass and a reference electrode in an
7. Scope integral unit. Place the electrodes in the beaker and standardize
7.1 This test method is applicable to the determination of the pH meter, using a reference buffer having a pH approxi-
acidity or alkalinity of all waters that are free of constituents mating that expected for the sample (see Test Methods D1293).
that interfere with electrometric pH measurements. It is used Rinse the electrodes, first with reagent water, then with a
for the development of a titration curve that will define portion of the sample. Following the final rinse, drain the
inflection points and indicate buffering capacity, if any. The beaker and electrodes completely.
12.2 Pipette 100 mL of the sample, adjusted, if necessary, to
4
room temperature, into the beaker through the third hole in the
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not stopper. Hold the tip of the pipette near the bottom of the
listed by the American Chemical Society, see Analar Standards for Laboratory beaker while discharging the sample.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopoeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 12.3 Measure the pH of the sample in accordance with Test
MD. Methods D1293.

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

15. Precision and Bias5 19. Apparatus

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.
20. Reagents
15.2 The collaborative test of this test method was per-
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
titration as directed in Practice E200 when an indicator is used
for sample titration.
5
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D19-1149. Contact ASTM Customer 20.3 Methyl Orange Indicator Solution (0.5 g/L)—Dissolve
Service at service@astm.org. 0.05 g of methyl orange in water and dilute to 100 mL.

3
 D1067 − 11
20.4 Methyl Purple Indicator Solution (l g/L)—Dissolve TABLE 2 Determination of Precision and Bias for Acidity and
0.45 g of dimethyl-aminoazobenzene-O-carboxylic acid, so- Alkalinity by Electrometric or Color-Change Titration
(Test Method B)
dium salt, in approximately 300 mL of water. To this solution
Amount Amount
add 0.55 g of a water-soluble blue dye-stuff, Color Index No. Added, Found, St So
Bias,
714,6,7 and dissolve. Dilute to 1 L with water. meq/L meq/L
%

20.5 Methyl Red Indicator Solution (1 g/L)—Dissolve 0.1 g Acidity

48.30 49.06 0.802 0.589 + 1.57
of water-soluble methyl red in water and dilute to 100 mL. 23.00 22.83 0.610 0.455 −0.74
17.10 16.84 0.334 0.146 −1.52
20.6 Phenolphthalein Indicator Solution (5 g/L)—Dissolve Alkalinity
0.5 g of phenolphthalein in 50 mL of ethyl alcohol (95 %) and 4.90 4.88 0.156 0.034 −0.41
dilute to 100 mL with water. 1.92 1.80 0.080 0.014 −6.25
0.51 0.50 0.044 0.024 −1.96
NOTE 4—Specially denatured ethyl alcohol conforming to Formula No.
3A or 30 of the U. S. Bureau of Internal Revenue may be substituted for
ethyl alcohol (95 %).
NOTE 5—Indicators are available commercially in prepared form. Acidity ~ or alkalinity! , meq/L ~ epm! 5 ~ AN/B ! 3 1000 (2)
20.7 Sodium Hydroxide, Standard (0.02 N)—See 11.2, ex- where:
cept that the alkali may be standardized by colorimetric 1000 = 1000 mL / liter
titration as directed in Practice E200 when an indicator is used A = standard acid or alkali required for the titration, mL,
for sample titration.
N = normality of the standard solution, and
21. Procedure
B = sample titrated, mL.
21.1 Depending on the method of titration to be used,
pipette 100 mL of the sample, adjusted, if necessary, to room 23. Report
temperature, into a 300-mL, tall-form beaker or a 250-mL, 23.1 Report the results of titration as follows: “The acidity
narrow-mouth Erlenmeyer flask. Hold the tip of the pipette (or alkalinity) to at °C = meq/L (epm),” indicating the pH and
near the bottom of the container while discharging the sample. the temperature at which it was determined, or the name of the
21.2 Titrate the aliquot electrometrically to the pH corre- indicator used, for example, “The acidity to methyl orange at
sponding to the desired end point (see Note 6). When using an °C = meq/L (epm).”
indicator, add 0.2 mL (see Note 7) and titrate with 0.02 N acid
24. Precision and Bias5
(for alkalinity) or 0.02 N NaOH solution (for acidity) until a
persistent color change is noted (see Note 8). Add the standard 24.1 The precision and bias data presented in Table 2 for
solution in small increments, swirling the flask vigorously after this test method meet the requirements of Practice D2777.
each addition. As the end point is approached, a momentary 24.2 The collaborative test of this test method was per-
change in color will be noted in that portion of the sample with formed in reagent waters by six laboratories using one operator
which the reagent first mixes. From that point on, make each, using three levels of concentration for both the acidity
dropwise additions. and alkalinity.
NOTE 6—The choice of end point will have been made to provide 24.3 Precision and bias for this test method conforms to
optimum data for the intended use or disposition of the water. When an Practice D2777–77, which was in place at the time of collab-
indicator is used, those listed in 20.1 and 20.3 through 20.6 are used most
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. requirements for interlaboratory studies of Committtee D19
NOTE 7—After some practice, slightly more or less indicator may be test methods.
preferred. The analyst must use the same quantity of phenolphthalein at all
times, however, because at a given pH, the intensity of one-color TEST METHOD C—COLOR-CHANGE TITRATION
indicators depends on the quantity.
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
waters bearing substantial amounts of ferrous iron or other
6
Refers to compounds, bearing such number, as described in “Color Index,” polyvalent cations in a reduced state.
Society of Dyers and Colourists, Yorkshire, England (1924).
7
The sole source of supply of the dye (Calcocid Blue AX Double) known to the 25.2 Because the oxidation and hydrolysis of ferrous iron
committee at this time is American Cyanamid Company, One Cyanamid Plaza, generate acidity, a reliable measure of acidity or alkalinity is
Wayne, NJ 07470. If you are aware of alternative suppliers, please provide this
obtained only when complete oxidation is achieved and hydro-
information to ASTM International Headquarters. Your comments will receive
careful consideration at a meeting of the responsible technical committee,1 which lysis to ferric salts is completed (see Appendix X3). In many
you may attend. instances, the concentration of ferrous iron is such that a 2-min

4
 D1067 − 11
boiling period is not sufficient to assure complete oxidation. In TABLE 3 Determination of Precision and Bias for Acidity by
this test method, hydrogen peroxide is added prior to boiling to Color-Change Titration After Hydrogen Peroxide Oxidation and
Boiling (Test Method C)
accelerate the chemical reactions needed for equilibrium.
Amount Amount
Bias,
25.3 This test method may be used to determine approxi- Added, Found, St So
%
mate alkali requirements for neutralization and to assure meq/L meq/L
comparability of results when both alkaline and acid flows are Acidity
48.30 49.06 1.28 0.43 +1.57
under consideration in mine drainage treatment. 23.00 23.00 0.46 0.37 0.00
0.07 0.15 0.12 0.69 +106.0
26. Summary of Test Method
26.1 The pH of the sample is determined. Standard acid is
added as needed to lower the pH to 4.0 or less. Hydrogen 31. Calculation
peroxide (H2O2) is added, the solution boiled, and finally either
31.1 Calculate the acidity in milliequivalents per liter using
titrated while hot to the phenolphthalein end point, or cooled
Eq 3 or Eq 4:
and titrated electrometrically with standard alkali to pH = 8.2,
31.1.1 Where no sulfuric acid is added:
the desired end point.

27. Interferences Acidity ~ boiled and oxidized! , meq/L ~ epm! 5 ~ BNb /S ! 3 1000 (3)
27.1 Natural color or the formation of a colored precipitate 31.1.2 Where sulfuric acid is added:
during boiling may mask the color change of the phenolphtha-
Acidity ~ boiled and oxidized! , meq/L ~ epm! 5 @ ~ BNb 2 ANa ! /S #
lein end point, requiring a pH meter for the titration. Suspended
solids may cause sluggishness in electrometric titrations; 3 1000 ~see Note 10! (4)
however, compensation is made by a 15-s pause between alkali where:
additions or by dropwise addition of titrant when the desig-
1000 = 1000 mL / liter
nated pH is approached. A = H2SO4 added to sample, mL,
27.2 The standard acid added prior to boiling neutralizes B = NaOH solution required for titration of sample, mL,
volatile components, for example, bicarbonates which contrib-
ute to the alkalinity and, hence, minimizes this source of error. Na = normality of the H2SO4,
Nb = normality of the NaOH solution, and
28. Apparatus S = sample used, mL.
NOTE 10—Minus acidity represents excess alkalinity contributed by
28.1 Electrometric pH Measurement Apparatus—See 10.1. constituents such as bicarbonates.

29. Reagents 32. Report

29.1 Hydrogen Peroxide (H2O2, 30 % Solution). 32.1 Report the results of titrations as follows: “The acidity
29.2 Phenolphthalein Indicator Solution (5 g/L)—See 20.6. (boiled and oxidized) to pH (or phenolphthalein) = meq/L
(epm).”
29.3 Sodium Hydroxide, Standard (0.02 N)—Prepare and
standardize as directed in Practice E200. 33. Precision and Bias5
29.4 Sulfuric Acid, Standard (0.02 N)—Prepare and stan- 33.1 The precision and bias data presented in Table 3 for
dardize as directed in Practice E200. this test method meet the requirements of Practice D2777.
NOTE 9—Hydrochloric acid of similar normality may be used instead of 33.2 The collaborative test of this test method was per-
sulfuric acid. Prepare and standardize in like manner. formed in reagent waters by six laboratories using one operator
each, using three levels of concentration for both the acidity
30. Procedure and alkalinity.
30.1 Pipette 50 mL of the sample into a 250-mL beaker. 33.3 Precision and bias for this test method conforms to
30.2 Measure the pH of the sample (see Test Methods Practice D2777 – 77, which was in place at the time of
D1293). If the pH is above 4.0, add 5-mL increments of collaborative testing. Under the allowances made in 1.4 of
standard H2SO4 to lower the pH to 4.0 or less (see Note 9). Practice D2777 – 08, these precision and bias data do meet
existing requirements for interlaboratory studies of D19 test
30.3 Add only 5 drops of H2O2.
methods.
30.4 Heat the sample to boiling and continue to boil for 2 to
4 min. 34. Quality Control
30.5 If the sample is discolored, cool to room temperature 34.1 In order to be certain that analytical values obtained
and titrate electrometrically with standard NaOH solution to using these test methods are valid and accurate within the
pH = 8.2, corresponding to the desired end point. If the sample confidence limits of the test, the following QC procedures must
is colorless, titrate to the phenolphthalein color change while be followed when analyzing acidity or alkalinity.
hot. 34.1.1 Calibration and Calibration Verification:

5
 D1067 − 11
34.1.1.1 Calibrate according to Test Methods D1293. 10 samples. The LCS must be taken through all of the steps of
34.1.1.2 Verify instrument calibration after standardization the analytical method, including sample pretreatment. The
by analyzing a pH solution. result obtained for the LCS shall fall within 615 % of the
34.1.1.3 If calibration cannot be verified, recalibrate the known concentration.
instrument. 34.1.3.2 If the result is not within the precision limit,
34.1.2 Initial Demonstration of Laboratory Capability: analysis of samples is halted until the problem is corrected, and
34.1.2.1 If a laboratory has not performed the test before, or either all the samples in the batch must be reanalyzed, or the
if there has been a major change in the measurement system, results must be qualified with an indication that they do not fall
for example, new analyst, new instrument, etc., a precision and within the performance criteria of the test method.
bias study must be performed to demonstrate laboratory 34.1.4 Duplicate:
capability. 34.1.4.1 To check the precision of sample analyses, analyze
34.1.2.2 Analyze seven replicates of a standard solution a sample in duplicate with each batch.
prepared from an Independent Reference Material containing a 34.1.4.2 Calculate the standard deviation of the duplicate
mid-range concentration acidity or alkalinity. The matrix and values and compare to the precision in the collaborative study
chemistry of the solution should be equivalent to the solution using an F test. Refer to 6.4.4 of Practice D5847 for informa-
used in the collaborative study. Each replicate must be taken tion on applying the F test.
through the complete analytical test method including any 34.1.4.3 If the result exceeds the precision limit, the batch
sample pretreatment steps. must be reanalyzed or the results must be qualified with an
34.1.2.3 Calculate the mean and standard deviation of the indication that they do not fall within the performance criteria
seven values and compare to the bias in Table 1, Table 2, or of the test method.
Table 3 (depending on the method used). This study should be
34.1.5 Independent Reference Material (IRM):
repeated until the recoveries are statistically equivalent to or
better than those in Table 1, Table 2, or Table 3. If a 34.1.5.1 In order to verify the quantitative value produced
concentration other than the recommended concentration is by the test method, analyze an Independent Reference Material
used, refer to Practice D5847 for information on applying the (IRM) submitted as a regular sample (if practical) to the
F test and t test in evaluating the acceptability of the mean and laboratory at least once per quarter. The concentration of the
standard deviation. IRM should be in the concentration mid-range for the method
34.1.3 Laboratory Control Sample (LCS): chose. The value obtained must fall within the control limits
34.1.3.1 To ensure that the test method is in control, analyze established by the laboratory.
a LCS containing a mid-range concentration of acidity or
alkalinity with each batch or 10 samples. If large numbers of 35. Keywords
samples are analyzed in the bath, analyze the LCS after every 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, analyses
X1.2 In addition to free hydroxide, alkalinity may be must be made without delay or results may be of little value.
produced by anions that tend to hydrolyze; these include Interpretation of acidity and alkalinity data should be made
carbonate, bicarbonate, silicate, phosphate, borate, arsenate, cautiously. For a more thorough understanding of the subject,
aluminate, possibly fluoride, and certain organic anions in it is recommended that the analyst review the literature8,9,10.
waste waters. All the effects due to these anions are lumped Then, the analyst may be able to develop an interpretation of
together in an alkalinity analysis. 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.

6
 D1067 − 11
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.

X2. INTERNAL ACID-BASE INDICATORS

X2.1 Table X2.1 is provided as a guide in the selection of 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 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
ferrous iron is rapidly oxidized to the ferric state, resulting in ion with hydrogen peroxide prior to titration:
the precipitation of Fe(OH)3: 2 Fe 12 1H 2 O 2 12H 11 →2 Fe 13 12H 2 O (X3.2)
2 Fe 12 11/2 O 2 14 OH 21 1H 2 O→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 twofold as ferric hydroxide:
problem. First, the solubility of ferrous ion at a pH of 8.2
(phenolphthalein end point) is appreciable and the full acidity Fe 13 13 OH 21 →Fe~ OH! 3 (X3.3)
potential of the water cannot be assessed by direct titration to Note that in Eq X3.2 and Eq X3.3, the net effect is that two
this end point. Second, at a pH of 8.2, soluble ferrous iron is hydroxyl ions are consumed for each ferrous ion originally
rapidly oxidized by atmospheric oxygen. Subsequent hydroly- present, although the end product in each case is ferric
sis of the resultant ferric ion immediately decreases the pH, 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
of waters containing no materials that buffer at the end point or measurement of acidity or alkalinity of waters containing
interfere with the titration due to color or precipitation, or other concentrations of slowly hydrolyzable materials sufficient to
reasons. significantly delay attainment of equilibrium conditions at a
titration end point. It is particularly applicable to mine
X4.1.3 The sample is titrated with standard acid or alkali to
drainage, industrial waste waters carrying waste acids, and
a predesignated pH, the end point being determined by
similar waters. Volatile components contributing to the acidity
comparison of the color developed by an added indicator with
the color of a standard buffer solution containing the same or alkalinity of the water may be lost during sample pretreat-
added indicator. ment.
X4.1.4 This test method was discontinued because there X4.2.3 The sample aliquot (acidified if alkaline) is boiled to
were insufficient laboratories interested in participating in accelerate chemical reactions for attaining equilibrium
another collaborative study to obtain the necessary precision conditions, cooled, and titrated with standard acid or alkali to
and bias as required by Practice D2777. a predesignated end point. Titration is carried out by means of

7
 D1067 − 11
an internal indicator using the color-change procedure de-
scribed in Test Method B (Electrometric or Color-Change
Titration).
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. (Approved April 1, 2011.)

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

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