ASTM D4458-15(2023)
(Test Method)Standard Test Method for Chloride Ions in Brackish Water, Seawater, and Brines
Standard Test Method for Chloride Ions in Brackish Water, Seawater, and Brines
SIGNIFICANCE AND USE
5.1 Chloride is present in virtually all oil field brines, seawaters, and many waste waters. Identification of the origin of the water and selection of its disposal method may be based upon the chloride content. The chloride content is also used to estimate the resistivity of formation waters and to differentiate between subsurface formations.
SCOPE
1.1 This test method2 is applicable to the measurement of chloride in highly mineralized waters such as oil field brines, seawater, and brackish water. The test method is based upon the titration of chloride with silver nitrate, using a visual indicator.
1.2 Samples containing from 10 mg to 150 mg of chloride can be analyzed by this test method. These levels are achieved by dilution as described in the test method.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 It is the user's responsibility to assure the validity of the method for untested types of water.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4458 − 15 (Reapproved 2023)
Standard Test Method for
Chloride Ions in Brackish Water, Seawater, and Brines
This standard is issued under the fixed designation D4458; 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.
1. Scope D3370 Practices for Sampling Water from Flowing Process
Streams
1.1 This test method is applicable to the measurement of
D5810 Guide for Spiking into Aqueous Samples
chloride in highly mineralized waters such as oil field brines,
D5847 Practice for Writing Quality Control Specifications
seawater, and brackish water. The test method is based upon
for Standard Test Methods for Water Analysis
the titration of chloride with silver nitrate, using a visual
indicator.
3. Terminology
1.2 Samples containing from 10 mg to 150 mg of chloride
3.1 Definitions—For definitions of terms used in this test
can be analyzed by this test method. These levels are achieved
method, refer to Terminology D1129.
by dilution as described in the test method.
4. Summary of Test Method
1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
4.1 This test method is based upon the Mohr procedure for
standard.
determining chloride ion with silver nitrate. The chloride reacts
with the silver ion before any silver chromate forms, due to the
1.4 It is the user’s responsibility to assure the validity of the
lower solubility of silver chloride. The potassium chromate
method for untested types of water.
indicator reacts with excess silver ion to form a red silver
1.5 This standard does not purport to address all of the
chromate precipitate. The end point is the appearance of the
safety concerns, if any, associated with its use. It is the
first permanent orange color.
responsibility of the user of this standard to establish appro-
4.2 This test method is suitable for analyzing solutions with
priate safety, health, and environmental practices and deter-
a pH between 6.0 and 8.5.
mine the applicability of regulatory limitations prior to use.
1.6 This international standard was developed in accor-
5. Significance and Use
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
5.1 Chloride is present in virtually all oil field brines,
Development of International Standards, Guides and Recom-
seawaters, and many waste waters. Identification of the origin
mendations issued by the World Trade Organization Technical
of the water and selection of its disposal method may be based
Barriers to Trade (TBT) Committee.
upon the chloride content. The chloride content is also used to
estimate the resistivity of formation waters and to differentiate
2. Referenced Documents
between subsurface formations.
2.1 ASTM Standards:
6. Interferences
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water 6.1 Sulfide, bromide, iodide, thiocyanate, cyanide,
D2777 Practice for Determination of Precision and Bias of phosphate, sulfite, carbonate, hydroxide, and iron interfere in
Applicable Test Methods of Committee D19 on Water this test method. Sulfide, sulfite, and thiosulfate can be re-
moved with a peroxide treatment, but usually no attempt is
made to remove bromide and iodide because they are usually
This test method is under the jurisdiction of ASTM Committee D19 on Water
present in insignificant quantities compared to chloride. If
and is the direct responsibility of D19.05 on Inorganic Constituents in Water.
necessary, the pH can be raised and the hydroxides of several
Current edition approved April 1, 2023. Published April 2023. Originally
approved in 1985. Last previous edition approved in 2015 as D4458 – 15. DOI: metals, including iron, can be filtered off. Iron, barium, lead,
10.1520/D4458-15R23.
and bismuth precipitate with the chromate indicator.
Hillebrand, W. F., Lundell, G. E. F., Bright, H. A., and Hoffman, J. I., Applied
Inorganic Analysis, 2nd Ed., 732, John Wiley & Sons, Inc., New York, NY, 1953.
7. Apparatus
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
7.1 Laboratory Glassware.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. 7.2 Buret, 25-mL capacity.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4458 − 15 (2023)
TABLE 1 Aliquot Size for Chloride Determination
7.3 Hotplate.
Specific Gravity Sample Dilution Equivalent Aliquot, mL
7.4 Magnetic Stirrer and TFE-fluorocarbon-Coated Stirring
1.000 to 1.010 None—Take 50 mL for 50
Bars.
analysis
1.010 to 1.025 None—Take 25 mL for 25
analysis
8. Reagents and Materials
1.025 to 1.050 Dilute 25 mL to 100 mL, 12.5
8.1 Purity of Reagents—Reagent grade chemicals shall be
take 50 mL
1.025 to 1.090 Dilute 25 mL to 100 mL, 6.25
used in all tests. Unless otherwise indicated, it is intended that
take 25 mL
all reagents shall conform to the specification of the Committee
1.090 to 1.120 Dilute 25 mL to 500 mL, 1.25
on Analytical Reagents of the American Chemical Society, take 25 mL
1.120 to 1.150 Dilute 25 mL to 1000 0.625
where such specifications are available. Other grades may be
mL, take 25 mL
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, reference
permanent orange color preceding a red precipitate. The
to water shall be understood to mean reagent water conforming
analyst must practice this titration to become familiar with this
to Specification D1193, Type I. Other reagent water types may
color.
be used provided it is first ascertained that the water is of
8.4.5 Determine the indicator blank by substituting 100 mL
sufficiently high purity to permit its use without adversely
of reagent grade water for the sample in 10.3 to 10.6.
affecting the precision and bias of the test method. Type III
8.4.6 The titre (T) of the silver nitrate solution is given in the
water was specified at the time of round robin testing of this
following equation:
test method.
mg Cl used
8.3 Silver Nitrate Solution, Standard (equivalent to 5 mg
− T 5 mL AgNO required 2 blank
Cl /mL)—Dissolve 23.9582 g of AgNO in approximately
700 mL of water. Add 1 drop concentrated nitric acid (HNO )
8.4.7 If the titre (T) of the solutions are not exactly 2.0 mg
−
and dilute to 1 L in a volumetric flask. The HNO will
or 5.0 mg of Cl per mL AgNO , it may be desirable to dilute
eliminate any precipitation of silver hydroxide which would
the solutions if they are too concentrated or add more silver
change the concentration. Standardize against sodium chloride
nitrate if too weak. In either case, restandardize the resulting
(NaCl) by the procedure described in 8.4. Store in an amber-
solution.
brown bottle to protect the solution from light.
8.5 Potassium or Sodium Chromate, Indicator Solution—
8.4 Silver Nitrate Solution, Standard (equivalent to 2 mg
Prepare a 5 % solution (5 g ⁄100 mL) and adjust the pH to 7.0
Cl/mL)—For lower chloride concentrations, this more dilute
with HNO (1 + 19) or NaHCO powder described in 8.6 and
3 3
standard will give a more accurate titration. Dissolve 9.5834 g
8.7.
of AgNO in approximately 700 mL of water. Add 1 drop
8.6 Sodium Bicarbonate (NaHCO )—Powder to adjust the
concentrated nitric acid (HNO ) and dilute to 1 L in a volu-
sample pH to 8.3.
metric flask. Standardize against sodium chloride (NaCl) by
8.7 Nitric Acid Solution (1 + 19)—Add 1 volume of
the procedure described below. Store in an amber-brown bottle
HNO (sp. gr. 1.42) to 19 volumes water.
to protect the solution from the light. 3
8.4.1 Dry 2 g to 6 g of high purity (minimum 99.5 %)
8.8 Filter Paper—Purchase suitable filter paper. The user
sodium chloride crystals at 110 °C for 2 h and cool in a
must first ascertain that the filter paper is of sufficient purity to
desiccator to room temperature.
use without adversely affecting the bias and precision of the
8.4.2 Weigh 1.6484 g of the NaCl crystals. Transfer the
test method.
crystals into a 1-L volumetric flask, dissolve, dilute, and mix
−
well. A quantity of 1 mL of this solution provides 1 mg of Cl .
9. Sampling
8.4.3 Pipet 50 mL aliquots of the NaCl solution to standard-
9.1 Collect the sample in accordance with Practices D3370.
−
ize the weaker AgNO solution (2 mg Cl /mL) and dilute to
100 mL with water. Use 100 mL of the NaCl solution to
10. Procedure
standardize the more concentrated AgNO solution (5 mg of
−
10.1 Filter (8.8) the sample to remove any insoluble or
Cl /mL).
suspended materials.
8.4.4 Add 1 mL of 5 % indicator solution (see 8.5), 1 g of
sodium bicarbonate powder, and titrate to the appearance of a
10.2 Pipet an aliquot of sample into a 150-mL Erlenmeyer
flask. Dilute to 100 mL with water. Refer to Table 1 for
approximate volume.
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
10.3 Measure the pH and adjust to near neutral.
Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by the American Chemical 10.4 Add 1 g of sodium bicarbonate and stir to dissolve. The
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
pH should be between 6.5 and 8.0.
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.