Standard Test Method for Chloride Ions in Brackish Water, Seawater, and Brines

SIGNIFICANCE AND USE
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 method 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 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 and health practices and determine the applicability of regulatory limitations prior to use.

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Publication Date
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D4458 − 09
StandardTest Method for
1
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 3. Terminology
2
1.1 This test method is applicable to the measurement of 3.1 Definitions—For definitions of terms used in this test
chloride in highly mineralized waters such as oil field brines, method, refer to Terminology D1129.
seawater, and brackish water. The test method is based upon
4. Summary of Test Method
the titration of chloride with silver nitrate, using a visual
indicator.
4.1 This test method is based upon the Mohr procedure for
determiningchlorideionwithsilvernitrate.Thechloridereacts
1.2 Samples containing from 10 to 150 mg of chloride can
withthesilverionbeforeanysilverchromateforms,duetothe
be analyzed by this test method. These levels are achieved by
lower solubility of silver chloride. The potassium chromate
dilution as described in the test method.
indicator reacts with excess silver ion to form a red silver
1.3 The values stated in SI units are to be regarded as
chromate precipitate. The end point is the appearance of the
standard. No other units of measurement are included in this
first permanent orange color.
standard.
4.2 Thistestmethodissuitableforanalyzingsolutionswith
1.4 Itistheuser’sresponsibilitytoassurethevalidityofthe
a pH between 6.0 and 8.5.
method for untested types of water.
5. Significance and Use
1.5 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
5.1 Chloride is present in virtually all oil field brines,
responsibility of the user of this standard to establish appro-
seawaters, and many waste waters. Identification of the origin
priate safety and health practices and determine the applica-
of the water and selection of its disposal method may be based
bility of regulatory limitations prior to use.
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.
3
2.1 ASTM Standards:
6. Interferences
D1129Terminology Relating to Water
6.1 Sulfide, bromide, iodide, thiocyanate, cyanide,
D1193Specification for Reagent Water
phosphate, sulfite, carbonate, hydroxide, and iron interfere in
D2777Practice for Determination of Precision and Bias of
this test method. Sulfide, sulfite, and thiosulfate can be re-
Applicable Test Methods of Committee D19 on Water
moved with a peroxide treatment, but usually no attempt is
D3370Practices for Sampling Water from Closed Conduits
made to remove bromide and iodide because they are usually
D5810Guide for Spiking into Aqueous Samples
present in insignificant quantities compared to chloride. If
D5847Practice for Writing Quality Control Specifications
necessary, the pH can be raised and the hydroxides of several
for Standard Test Methods for Water Analysis
metals, including iron, can be filtered off. Iron, barium, lead,
and bismuth precipitate with the chromate indicator.
1
This test method is under the jurisdiction ofASTM Committee D19 on Water
7. Apparatus
and is the direct responsibility of D19.05Inorganic Constituents in Water.05 on
Inorganic Constituents in Water.
7.1 Laboratory Glassware.
Current edition approved Oct. 1, 2009. Published October 2009. Originally
approved in 1985. Last previous edition approved in 2005 as D4458–05. DOI: 7.2 Buret, 25-mL capacity.
10.1520/D4458-09.
7.3 Hotplate.
2
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.
7.4 Magnetic Stirrer and TFE-fluorocarbon-Coated Stirring
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Bars.
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. 8. Reagents
*A Summary of Changes section appears at the end of this standard
Copyright ©ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA19428-2959. United States
1

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D4458 − 09
TABLE 1 Aliquot Size for Chloride Determination
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that Specific Gravity Sample Dilution EquivalentAliquot, mL
allreagentsshallconformtothespecificationoftheCommittee 1.000 to 1.010 None—Take 50 mL for 50
analysis
on Analyti
...

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately,ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D4458–05 Designation:D4458–09
Standard Test Method for
1
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope*
2
1.1 Thistestmethod isapplicabletothemeasurementofchlorideinhighlymineralizedwaterssuchasoilfieldbrines,seawater,
and brackish water. The test method is based upon the titration of chloride with silver nitrate, using a visual indicator.
1.2 Samplescontainingfrom10to150mgofchloridecanbeanalyzedbythistestmethod.Theselevelsareachievedbydilution
as described in the test method.
1.3It is the user’s responsibility to assure the validity of the method for untested types of water.
1.4
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 and health practices and determine the applicability of regulatory
limitations prior to use.
2. Referenced Documents
3
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
D5810 Guide for Spiking into Aqueous Samples
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
3. Terminology
3.1 Definitions: —ForFor definitions of terms used in this test method, refer to Terminology D1129.
4. Summary of Test Method
4.1 ThistestmethodisbasedupontheMohrprocedurefordeterminingchlorideionwithsilvernitrate.Thechloridereactswith
the silver ion before any silver chromate forms, due to the lower solubility of silver chloride. The potassium chromate indicator
reactswithexcesssilveriontoformaredsilverchromateprecipitate.Theendpointistheappearanceofthefirstpermanentorange
color.
4.2 This test method is suitable for analyzing solutions with a pH between 6.0 and 8.5. 8.5.
5. Significance and Use
5.1 Chlorideispresentinvirtuallyalloilfieldbrines,seawaters,andmanywastewaters.Identificationoftheoriginofthewater
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.
6. Interferences
6.1 Sulfide, bromide, iodide, thiocyanate, cyanide, phosphate, sulfite, carbonate, hydroxide, and iron interfere in this test
1
This test method is under the jurisdiction ofASTM Committee D19 on Water and is the direct responsibility of SubcommiteeD19.05 D19.05 Inorganic Constituents in
Water.05 on Inorganic Constituents in Water.
Current edition approved Aug. 15, 2005.Oct. 1, 2009. Published August 2005.October 2009. Originally approved in 1985. Last previous edition approved in 19942005
as D4458–85 (1999). D4458–05. DOI: 10.1520/D4458-059.
2
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.
3
ForreferencedASTMstandards,visittheASTMwebsite,www.astm.org,orcontactASTMCustomerServiceatservice@astm.org.For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on 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.
1

---------------------- Page: 1 ----------------------
D4458–09
method. Sulfide, sulfite, and thiosulfate can be removed with a peroxide treatment, but usually no attempt is made to remove
bromide and iodide because they are usually present in insignificant quantities compared to chloride. If necessary, the pH can be
raisedandthehydroxidesofseveralmetals,includingiron,canbefilteredoff.Iron,barium,lead,andbismuthprecipitatewiththe
chromate indicator.
7. Apparatus
7.1 Laboratory Glassware.
7.2 Buret, 25-mL capacity.
7.3 Hotplate.
7.4 Magnetic Stirrer and TFE-flu
...

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