Professional Documents
Culture Documents
ASTM D512 Cloruros
ASTM D512 Cloruros
Designation: D 512 – 04
This standard has been approved for use by agencies of the Department of Defense.
1.1 These test methods cover the determination of chloride for Standard Test Methods for Water Analysis
ion in water, wastewater (Test Method C only), and brines. The E 200 Practice for Preparation, Standardization, and Stor-
following three test methods are included: age of Standard and Reagent Solutions for Chemical
Sections
Analysis
Test Method A (Mercurimetric Titration) 7 to14
Test Method B (Silver Nitrate Titration) 15 to 21
3. Terminology
Test Method C (Ion-Selective Electrode Method) 22 to 29 3.1 Definitions—For definitions of terms used in these test
1.2 Test Methods A, B, and C were validated under Practice methods, refer to Terminologies D 1129 and D 4127.
D2777 – 77, and only Test Method B conforms also to Practice
4. Significance and Use
D 2777 – 86. Refer to Sections 14, 21, and 29 for further
information. 4.1 Chloride ion is under regulation in water, and must,
1.3 This standard does not purport to address all of the therefore, be measured accurately. It is highly detrimental to
safety concerns, if any, associated with its use. It is the high-pressure boiler systems and to stainless steel, so monitor-
responsibility of the user of this standard to establish appro- ing is essential for prevention of damage. Chloride analysis is
priate safety and health practices and determine the applica- widely used as a tool for estimating the cycles of concentration,
bility of regulatory limitations prior to use. For a specific such as in cooling tower applications. Processing waters and
hazard statement, see 26.1.1. pickling solutions used in the food processing industries also
1.4 A former colorimetric test method was discontinued. require dependable methods of analysis for chloride.
Refer to Appendix X1 for historical information.
5. Purity of Reagents
2. Referenced Documents 5.1 Reagent grade chemicals shall be used in all tests.
2.1 ASTM Standards: 2 Unless otherwise indicated, it is intended that all reagents shall
D 1066 Practice for Sampling Steam conform to the specifications of the Committee on Analytical
D 1129 Terminology Relating to Water Reagents of the American Chemical Society, where such
D 1193 Specification for Reagent Water specifications are available.3 Other grades may be used, pro-
D 2777 Practice for Determination of Precision and Bias of vided it is first ascertained that the reagent is of sufficiently
Applicable Methods of Committee D19 on Water high purity to permit its use without lessening the accuracy of
D 3370 Practices for Sampling Water from Closed Conduits the determination.
D 4127 Terminology Used with Ion-Selective Electrodes 5.2 Purity of Water— Unless otherwise indicated, refer-
D 5810 Guide for Spiking into Aqueous Samples ences to water shall be understood to mean Type I reagent
water conforming to Specification D 1193. Other reagent water
types may be used provided it is first ascertained that the water
1
These test methods are under the jurisdiction of ASTM Committee D19 on
is of sufficiently high purity to permit its use without adversely
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
Constituents in Water.
3
Current edition approved July 1, 2004. Published July 2004. Originally approved Reagent Chemicals, American Chemical Society Specifications, American
in 1938. Last previous edition approved in 1989 as D 512 – 89 (1999). 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 service@astm.org. 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. Pharmaceutical Convention, Inc. (USPC), Rockville,
the ASTM website. MD.
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
D 512 – 04
affecting the precision and bias of the test method. Type II with water to 1 L. Filter if necessary, and standardize against
water was specified at the time of round robin testing of this the standard sodium chloride (NaCl) solution, using the pro-
test method. cedure described in Section 12 (see Note 1).
6. Sampling NOTE 1—Sharpness of End Point—The end point, while sharp, can be
improved somewhat for certain types of water by adding several drops of
6.1 Collect the sample in accordance with Practice D 1066 a 0.05-g/L solution of xylene cyanole FF or alphazurine blue-green dye
and Practices D 3370, as applicable. (color index 714) to the titration sample.
TEST METHOD A—MERCURIMETRIC 11.4 Mixed Indicator Solution 5—Dissolve 0.5 g of crystal-
TITRATION 4 line diphenylcarbazone and 0.05 g of bromophenol blue
powder in 75 mL of ethyl alcohol (95 %), and dilute to 100 mL
7. Scope with the alcohol (Note 2). Store in a brown bottle and discard
7.1 This test method can be used to determine chloride ion after 6 months (Note 3).
in water, provided interferences are absent (see Section 9). NOTE 2—Methanol, isopropanol, or ethanol denatured with either
7.2 Though not specified in the research report, the preci- methanol or isopropanol (Formula 3A) may be used if pure ethyl alcohol
sion statement is presumed to have been obtained using Type II is not available. Other denatured ethanol formulae are not suitable.
reagent water. It is the responsibility of the analyst to assure the NOTE 3—Liquid indicator generally deteriorates to the point that it
yields no end-point color after 12 to 18 months of storage. High
validity of this test method for untested matrices.
temperature (above 37.8°C (100°F)) and exposure to bright light may
7.3 This test method was validated for the concentration shorten storage life. A dry powder mixture of the two indicator ingredients
range 8.0 to 250 mg/L Cl−. is stable for much longer periods. Both the powder mixture (capsule form)
and the liquid indicator are available commercially.
8. Summary of Test Method
11.5 Nitric Acid (3 + 997)—Mix 3 volumes of concen-
8.1 Dilute mercuric nitrate solution is added to an acidified
trated nitric acid (HNO3, sp gr 1.42) with 997 volumes of
sample in the presence of mixed diphenylcarbazone-
water.
bromophenol blue indicator. The end point of the titration is the
11.6 pH Indicating Paper, long-range type, covering a pH
formation of the blue-violet mercury diphenylcarbazone com-
range 1 to 11.
plex.
11.7 Sodium Chloride Solution, Standard (0.025N)—Dry
9. Interferences several grams of sodium chloride (NaCl) for 1 h at 600°C.
Dissolve 1.4613 g of the dry salt in water, and dilute to 1 L at
9.1 The anions and cations generally found in water offer no
25°C in a volumetric flask.
interference. Zinc, lead, nickel, and ferrous and chromous ions
11.8 Sodium Hydroxide Solution (10 g/L)—Dissolve 10 g of
affect solution and end-point colors, but do not reduce the
sodium hydroxide (NaOH) in water and dilute to 1 L.
accuracy of the titration when present in concentrations up to
100 mg/L. Copper is tolerable up to 50 mg/L. Titration in the 12. Procedure
presence of chromate ion requires indicator with extra back- 12.1 Use a volume of sample such that it will contain not
ground color (alphazurine) and prior reduction for concentra- more than 20 mg of chloride ion, diluting the sample with
tions above 100 mg/L. Ferric ion above 10 mg/L must be water to approximately 50-mL volume if necessary. Determine
reduced before titration, and sulfite ion must be oxidized. an indicator blank on 50 mL of chloride-free water, applying
Bromide and fluoride will be partially titrated with the chlo- the same procedure followed for the sample.
ride. Quaternary ammonium salts also interfere if present in 12.2 Add 5 to 10 drops of mixed indicator solution, and
significant amounts (1 to 2 mg/L). Deep color may also shake or swirl the flask. If a blue-violet or red color develops,
interfere. add HNO3 (3 + 997) dropwise until the color changes to
10. Apparatus yellow. Add 1 mL of excess acid. If a yellow or orange color
forms immediately on addition of the mixed indicator, add
10.1 Microburet, 1 or 5-mL, with 0.01-mL graduation NaOH solution (10 g/L) dropwise until the color changes to
intervals. blue-violet; then add HNO3 (3 + 997) dropwise until the color
11. Reagents and Materials changes to yellow and further add 1 mL excess of acid (Note
4).
11.1 Hydrogen Peroxide (30 % H2O2).
11.2 Hydroquinone Solution (10 g/L)—Dissolve 1 g of NOTE 4—The prescribed acidification provides a satisfactory pH range
purified hydroquinone in water and dilute to 100 mL. from 3.0 to 3.5. Acidified samples on which electrometric pH measure-
ments have been made shall not be used for chloride determinations,
11.3 Mercuric Nitrate Solution, Standard (0.025N)—
because the use of the calomel reference electrode may introduce error due
Dissolve 4.2830 g of mercuric nitrate (Hg(NO3)2·H2O) in 50 to chloride contamination. For precise pH adjustment of samples having a
mL of water acidified with 0.5 mL of concentrated nitric acid low-chloride concentration, instrumental measurements may be made on
(HNO3, sp gr 1.42). Dilute the acidified Hg(NO3)2 solution one sample aliquot to determine treatment needed for another to be used
for the chloride test.
4
For information of interest in connection with this test method, and supporting
5
data, refer to Clark, F. E., “Determination of Chloride in Water,” Analytical This diphenylcarbazone 1-bromophenol blue indicator is covered by U.S.
Chemistry, Vol 22, April 1950, pp. 553–555, and Vol 22, November 1950, p. 1458. Patent No. 2,784,064.
--``````-`-`,,`,,`,`,,`---
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
D 512 – 04
12.3 Titrate the solution and a blank with 0.025 N Hg(NO3)2 X = concentration of chloride ion determined.
solution until a blue-violet color, as viewed by transmitted 14.2 Bias Statement— Recoveries of known amounts of
light, persists throughout the solution (Note 5). Record the chloride were as follows:
millilitres of Hg(NO3)2 solution added in each case. Statistically
Amount Added, Amount Found, Significant (95 %
NOTE 5—The use of indicator modifications and the presence of heavy mg/L mg/L 6 % Bias Confidence Level)
metal ions can change solution colors without affecting accuracy of the 250 248 −0.80 no
determination. For example, solutions containing alphazurine may be 80.0 79.3 −0.88 no
bright blue when neutral, grayish purple when basic, blue-green when 8.00 7.51 −6.13 yes
acidic, and blue-violet at the chloride end point. Solutions containing
about 100 mg/L nickel ion and normal mixed indicator are purple when
14.3 The information presented in 14.1 and 14.2 is derived
neutral, green when acid, and gray at the chloride end point. When from round-robin testing in which five laboratories, including
applying this test method to samples that contain colored ions or that seven operators, participated. Though not clearly specified in
require modified indicator, it is recommended that the operator be familiar the test report, the matrix is presumed to be Type II reagent
with the specific color changes involved by experimenting with solutions water. Of seven data sets ranked as described in Practice
prepared as standards for comparison of color effects. D 2777, none was rejected, nor were any data points deter-
12.4 If chromate ion is present in the absence of iron and in mined to be “outliers.” Three sample levels were run on at least
concentration less than 100 mg/L, use the alphazurine modified three days. The method of “least squares” was used to
mixed indicator (Note 1) and acidify the sample as described in determine the precision statement, with correlation of 0.7394
12.2 but to pH 3 as indicated by pH indicating paper. Titrate the for SO and 0.9993 for ST.
solution as described in 12.3, but to an olive-purple end point. 14.4 It is the responsibility of the analyst to assure the
12.5 If chromate ion is present in the absence of iron and in validity of this test method for untested matrices.
concentration greater than 100 mg/L, add 2 mL of fresh 14.5 Precision and bias for this test method conforms to
hydroquinone solution and proceed as described in 12.2 and Practice D 2777 – 77, which was in place at the time of
12.3. collaborative testing. Under the allowances made in 1.5 of
12.6 If ferric ion is present in the absence or presence of Practice D 2777 – 86, these precision and bias data do meet
chromate ions, use a sample of such volume as to contain no existing requirements for interlaboratory studies of Committee
more than 2.5 mg of ferric ion or of ferric ion plus chromate D–19 test methods.
ion. Add 2 mL of fresh hydroquinone solution, and proceed as
--``````-`-`,,`,,`,`,,`---
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
where: analyst to assure the validity of this test method for untested
V 1 = standard Hg(NO3)2 solution required for titration of matrices.
the sample, mL, 15.3 This test method was validated for the concentration
V2 = standard Hg(NO3)2 solution required for titration of range 8.0 to 250 mg/L Cl−.
the blank, mL,
N = normality of the Hg(NO3)2 solution, and 16. Summary of Test Method
S = sample used in 12.1, mL.
16.1 Water adjusted to approximately pH 8.3 is titrated with
14. Precision and Bias 6 silver nitrate solution in the presence of potassium chromate
indicator. The end point is indicated by persistence of the
14.1 Precision Statement—The precision of this test method
brick-red silver chromate color.
may be expressed as follows:
ST 5 0.023X 1 0.43 17. Interferences
17.1 Bromide, iodide, and sulfide are titrated along with the
SO 5 0.002X 1 0.46 chloride. Orthophosphate and polyphosphate interfere if
where: present in concentrations greater than 250 and 25 mg/L,
S T = overall precision, mg/L, respectively. Sulfite and objectionable color or turbidity must
SO = single-operator precision, mg/L, and be eliminated. Compounds which precipitate at pH 8.3 (certain
hydroxides) may cause error by occlusion.
6
Supporting data are available from ASTM Headquarters. Request RR: D19-
7
1076. Mohr, F., ANN., 97, 335 (1856).
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
18. Reagents V2 = standard solution, AgNO3 added in titrating the
18.1 Hydrogen Peroxide (30 %) (H2O2). sample prepared in 19.3, mL,
18.2 Phenolphthalein Indicator Solution (10 g/L)—Prepare N = normality of standard AgNO 3 solution, and
as directed in Practice E 200. S = original sample in the 50-mL test specimen prepared
18.3 Potassium Chromate Indicator Solution—Dissolve 50 in 19.1, mL.
g of potassium chromate (K2CrO4) in 100 mL of water, and add 6
silver nitrate (AgNO3) until a slight red precipitate is produced. 21. Precision and Bias
Allow the solution to stand, protected from light, for at least 24 21.1 Precision—The precision of this test method may be
h after the addition of AgNO3. Then filter the solution to expressed as follows:
remove the precipitate, and dilute to 1 L with water. ST 5 0.013X 1 0.70
18.4 Standard Solution, Silver Nitrate (0.025 N)—Crush
approximately 5 g of silver nitrate (AgNO 3) crystals and dry to SO 5 0.007X 1 0.53
constant weight at 40°C. Dissolve 4.2473 g of the crushed,
--``````-`-`,,`,,`,`,,`---
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
--``````-`-`,,`,,`,`,,`---
D 512 – 04
FIG. 1 Interlaboratory Precision for Chloride Found in Reagent Water (Ion Selective Electrode)
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
FIG. 2 Interlaboratory Precision for Chloride Found in Selected Water Matrices (Ion Selective Electrode)
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
30.3 Initial Demonstration of Laboratory Capability 30.6.3 Calculate the percent recovery of the spike (P) using
30.3.1 If a laboratory has not performed the test before, or if the following formula:
there has been a major change in the measurement system, for
P 5 100 [A~Vs 1 V! – BVs# / CV
example, new analyst, new instrument, and so forth, a precision
and bias study must be performed to demonstrate laboratory where:
capability.
30.3.2 Analyze seven replicates of a standard solution
prepared from an Independent Reference Material containing a A = analyte concentration (mg/L) in spiked sample,
mid-range concentration of chloride. The matrix and chemistry B = analyste concentration (mg/L) in unspiked sample,
C = concentration (mg/L) of analyte in spiking solution,
of the solution should be equivalent to the solution used in the
Vs = volume (mL) of sample used, and
collaborative study. Each replicate must be taken through the V = volume (mL) added with spike.
complete analytical test method including any sample preser-
vation and pretreatment steps. The replicates may be inter- 30.6.4 The percent recovery of the spike shall fall within the
spersed with samples. limits, based on the analyte concentration, listed in Guide D
30.3.3 Calculate the mean and standard deviation of the 5810, Table 1. If the percent recovery is not within these limits,
seven values and compare to the acceptable ranges of bias in a matrix interference may be present in the sample selected for
sections 14.2, 21.2 and 29.2. This study should be repeated spiking. Under these circumstances, one of the following
until the recoveries are within the limits given in sections 14.2, remedies must be employed: the matrix interference must be
21,.2 and 29.2. If a concentration other than the recommended removed, all samples in the batch must be analyzed by a test
concentration is used, refer to Practice D 5847 for information method not affected by the matrix interference, or the results
on applying the F test and t test in evaluating the acceptability must be qualified with an indication that they do not fall within
of the mean and standard deviation. the performance criteria of the test method.
30.4 Laboratory Control Sample (LCS) NOTE 9—Acceptable spike recoveries are dependent on the concentra-
30.4.1 To ensure that the test method is in control, analyze tion of the component of interest. See Guide D 5810 for additional
a LCS containing a mid-range concentration of chloride with information.
each batch or 10 samples. If large numbers of samples are
30.7 Duplicate
analyzed in the batch, analyze the LCS after every 10 samples.
The LCS must be taken through all of the steps of the analytical 30.7.1 To check the precision of sample analyses, analyze a
method including sample preservation and pretreatment. The sample in duplicate with each batch. If the concentration of
result obtained for the LCS shall fall within 6 15 % of the chloride is less than five times the detection limit for the
known concentration. method, a matrix spike duplicate (MSD) should be used.
30.4.2 If the result is not within these limits, analysis of 30.7.2 Calculate the standard deviation of the duplicate
samples is halted until the problem is corrected, and either all values and compare to the precision in the collaborative study
the samples in the batch must be reanalyzed, or the results must using an F test. Refer to 6.4.4 of Practice D 5847 for
be qualified with an indication that they do not fall within the information on applying the F test.
performance criteria of the test method. 30.7.3 If the result exceeds the precision limit, the batch
30.5 Method Blank must be reanalyzed or the results must be qualified with an
30.5.1 Analyze a reagent water test blank with each batch. indication that they do not fall within the performance criteria
The concentration of chloride found in the blank should be less of the test method.
than 0.5 times the lowest calibration standard. If the concen- 30.8 Independent Reference Material (IRM)
tration of chloride is found above this level, analysis of
30.8.1 In order to verify the quantitative value produced by
samples is halted until the contamination is eliminated, and a
--``````-`-`,,`,,`,`,,`---
APPENDIX
(Nonmandatory Information)
X1.1 Former Test Method C (Colorimetric): which in turn combines with ferric to form red ferric thiocy-
X1.1.1 This test method was discontinued in 1988. The test anate. The intensity of the color, which is proportional to the
method may be found in its entirety in the 1988 Annual Book concentration of the chloride ions, is measured photometrically
of ASTM Standards, Vol 11.01. at a wavelength of 463 nm, or by visual comparison with
X1.1.2 This test method may be applied to waters contain- standard solutions.
ing chloride ion in concentrations from 0.10 to 10 mg/L. X1.1.4 This test method was discontinued because there
X1.1.3 Solutions of ferric ammonium sulfate and mercuric were insufficient laboratories interested in participating in
//^:^^#^~^^""~:$"^#$:~@""#:$@~*:"@@~~"~~$"^^:@^:~$:@:\\
thiocyanate are added to the sample. The chloride ion reacts another collaborative study to obtain the necessary precision
with the mercuric thiocyanate to produce thiocyanate ion and bias as required by Practice D 2777.
SUMMARY OF CHANGES
Subcommittee D19 has identified the location of selected changes to this standard since the last issue
(D 512 – 89 (1999)) that may impact the use of this standard.
(1) Guide D 5810, Practice D 5847, and Practice E 200 were (3) The reference to Practice E 200 in section 18.2 was
added to Section 2. corrected.
(2) Section 5.2 was modified to use Type I water. (4) Section 30 was added.
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
--``````-`-`,,`,,`,`,,`---
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.
This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org).