ASTM E1754-17a

Standard Test Method for Determination of Low Levels of Water in Liquid Chlorine By Infrared Spectrophotometry

SIGNIFICANCE AND USE
4.1 Trace amounts of water may be detrimental to the use of chlorine in some applications. The amount of water in the chlorine must be known to prevent problems during its use.
SCOPE
1.1 This test method covers the determination of the content of water in liquid chlorine in the concentration range of 0.5 to 15 mg/kg (ppm).  
1.2 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.  
1.3 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.4 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. See Section 7 for specific hazards statements.  
1.5 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

• Status: Published
• Publication Date: 30-Jun-2017
• ICS: 71.040.50 - Physicochemical methods of analysis
• ICS: 71.100.20 - Gases for industrial application
• Technical Committee: D16 - Aromatic, Industrial, Specialty and Related Chemicals
• Drafting Committee: D16.13 - Chlorine

Relations

• Replaces: ASTM E1754-17 - Standard Test Method for Determination of Low Levels of Water in Liquid Chlorine By Infrared Spectrophotometry
• Effective Date: 01-Jul-2017
• Refers: ASTM E806-17 - Standard Test Method for Carbon Tetrachloride and Chloroform in Liquid Chlorine by Direct Injection (Gas Chromatographic Procedure)
• Effective Date: 01-Mar-2017
• Refers: ASTM D6809-02(2016) - Standard Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
• Effective Date: 01-Nov-2016
• Refers: ASTM E806-08 - Standard Test Method for Carbon Tetrachloride and Chloroform in Liquid Chlorine by Direct Injection (Gas Chromatographic Procedure)
• Effective Date: 15-Dec-2008
• Refers: ASTM D6809-02(2007) - Standard Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
• Effective Date: 01-Jun-2007
• Refers: ASTM D1193-06 - Standard Specification for Reagent Water
• Effective Date: 01-Mar-2006
• Refers: ASTM D6809-02 - Standard Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
• Effective Date: 10-Jun-2002
• Refers: ASTM D1193-99 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999
• Refers: ASTM D1193-99e1 - Standard Specification for Reagent Water
• Effective Date: 10-Feb-1999

Overview

ASTM E1754-17a is the internationally recognized standard test method for the determination of low levels of water in liquid chlorine by infrared spectrophotometry. Managed by ASTM International, this standard enables highly accurate measurement of water concentrations in liquid chlorine within a range of 0.5 to 15 mg/kg (ppm). Understanding and controlling water contamination in chlorine is critical, as trace amounts can negatively impact various industrial processes and end-use applications. Compliance with ASTM E1754-17a ensures quality assurance and process safety in industries relying on chlorine.

Key Topics

• Purpose and Significance: Moisture control in liquid chlorine is essential for preventing equipment damage, corrosion, and undesirable chemical reactions during chlorine usage. The test ensures trace levels of water are reliably identified to maintain product integrity.
• Measurement Range: The standard covers water determination in concentrations from 0.5 to 15 mg/kg (parts per million), supporting high-sensitivity detection in quality-critical environments.
• Test Methodology: Using an infrared spectrophotometer, the method involves analyzing the absorbance at specific wavenumber bands indicative of water presence. Calibration is performed using known water concentrations to ensure accuracy.
• Apparatus and Materials: Required equipment includes an FTIR spectrometer, specialized infrared sample cell, and high-purity reagents. Proper sampling techniques and cylinder preparation are emphasized for reliable results.
• Safety Considerations: The standard mandates strict adherence to safety practices due to the toxic and reactive nature of chlorine. It requires thorough knowledge of handling procedures, proper ventilation, and use of protective gear.
• Quality Assurance: Laboratories implementing this test method must maintain a robust quality control system, referencing either established in-house protocols or ASTM guidance for statistical quality control.

Applications

Following ASTM E1754-17a delivers strong practical value in various industrial and environmental settings:

• Chlorine Production and Distribution: Ensures bulk liquid chlorine supplied to customers meets strict water content requirements, reducing the risk of corrosion or unfavorable reactions in end-use environments.
• Chemical Manufacturing: Supports reliable process control in the synthesis of products where chlorine purity is critical, helping manufacturers avoid costly downtimes and product failures.
• Water Treatment Facilities: Assists facilities in verifying that chlorine used in disinfection processes is of appropriate quality and prevents introduction of excess water that could affect treatment performance.
• Quality Control in Laboratories: Provides a validated analytical procedure for testing and certifying chlorine products, enabling laboratories to provide reliable certification data for regulatory or commercial needs.
• Regulatory Compliance: Assists organizations in meeting industry, contractual, and regulatory requirements concerning chlorine purity and water content.

Related Standards

For comprehensive management of liquid chlorine analysis and safety, consider the following standards commonly referenced in conjunction with ASTM E1754-17a:

• ASTM D1193 - Specification for Reagent Water: Establishes criteria for water purity, supporting the preparation of calibration standards.
• ASTM D6809 - Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials: Provides best practices for statistical QC in chemical analysis.
• ASTM E806 - Test Method for Carbon Tetrachloride and Chloroform in Liquid Chlorine by Direct Injection (Gas Chromatographic Procedure): Related to the detection of other trace impurities in chlorine.
• 49 CFR 173 - U.S. Code of Federal Regulations, Title 49 (Transportation): Contains federal requirements for the shipment and handling of compressed gases, including chlorine.

Conclusion

Implementing ASTM E1754-17a is essential for industries and laboratories involved with liquid chlorine to ensure product quality, safety, and regulatory compliance. This standard provides a robust, detailed framework for detecting and controlling water contamination in liquid chlorine, utilizing advanced infrared spectrophotometry and quality control protocols for reliable and accurate results.

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: E1754 − 17a
Standard Test Method for
Determination of Low Levels of Water in Liquid Chlorine By
Infrared Spectrophotometry
This standard is issued under the fixed designation E1754; 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* D6809 Guide for Quality Control and Quality Assurance
Procedures for Aromatic Hydrocarbons and Related Ma-
1.1 This test method covers the determination of the content
terials
of water in liquid chlorine in the concentration range of 0.5 to
E806 Test Method for Carbon Tetrachloride and Chloroform
15 mg/kg (ppm).
in Liquid Chlorine by Direct Injection (Gas Chromato-
1.2 The values stated in SI units are to be regarded as
graphic Procedure)
standard. The values given in parentheses are for information 3
2.2 Federal Standards:
only.
49 CFR 173 Code of Federal Regulations Title 49 Transpor-
1.3 Review the current Safety Data Sheets (SDS) for de- tation: Shippers’General Requirements for Shipments and
Packaging, including Sections:
tailed information concerning toxicity, first aid procedures, and
safety precautions. 173.304 Charging of Cylinders with Liquefied Compressed
Gas
1.4 This standard does not purport to address all of the
173.314 Requirements for Compressed Gases in Tank Cars
safety concerns, if any, associated with its use. It is the
173.315 Compressed Gases in Cargo Tanks and Portable
responsibility of the user of this standard to establish appro-
Tank Containers
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
3. Summary of Test Method
See Section 7 for specific hazards statements.
3.1 A sample of liquid chlorine is introduced into a special
1.5 This international standard was developed in accor-
infrared cell and maintained as a liquid under its own pressure.
dance with internationally recognized principles on standard-
A spectrometer scans from 400 to 4400 wavenumbers of the
ization established in the Decision on Principles for the
infrared transmission spectrum of liquid chlorine. This spec-
Development of International Standards, Guides and Recom-
trum is then ratioed to one obtained of the nitrogen-filled
mendations issued by the World Trade Organization Technical
infrared cell previously. The ratioed spectrum is converted to
Barriers to Trade (TBT) Committee.
absorbance, and the net absorbance of the water band at 1596
wavenumbers, relative to a reference at 1663 wavenumbers, is
2. Referenced Documents
determined. The amount of water corresponding to this net
2.1 ASTM Standards:
absorbance is determined from a calibration curve prepared
D1193 Specification for Reagent Water
from the infrared absorbances of standards that contain known
concentrations of water in liquid chlorine.
This test method is under the jurisdiction of ASTM Committee D16 on
4. Significance and Use
Aromatic, Industrial, Specialty and Related Chemicals and is the direct responsi-
4.1 Trace amounts of water may be detrimental to the use of
bility of Subcommittee D16.13 on Chlorine.
Current edition approved July 1, 2017. Published July 2017. Originally approved
chlorine in some applications. The amount of water in the
in 1995. Last previous edition approved in 2017 as E1754 – 17. DOI: 10.1520/
chlorine must be known to prevent problems during its use.
E1754-17a.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Available from U.S. Government Printing Office, Superintendent of
Standards volume information, refer to the standard’s Document Summary page on Documents, 732 N. Capitol St., NW, Washington, DC 20401-0001, http://
the ASTM website. www.access.gpo.gov.
*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
E1754 − 17a
5. Apparatus
5.1 Infrared Spectrometer, capable of measurements in the
1600 wavenumber region. An FTIR with 4 wavenumber
resolution is the instrument of choice, but dispersive instru-
ments may also be used to achieve similar results.
5.2 Special Infrared Cell (see Fig. 1), neither cell size nor
pathlength are critical to the analysis, but sensitivity and limit
of detection are dependent on pathlength. The concentration
range reported in the scope is achievable with a 60-mm
pathlength cell constructed with:
FIG. 1(a) Pipe Adapter
FIG. 1(b) Air Cap Detail
NOTE 1—Drawing not to scale.
FIG. 1 Infrared Cell
E1754 − 17a
FIG. 1(e) Insert Detail
FIG. 1(c) Body Detail
FIG. 1(f) Flange Detail
FIG. 1(d) Gasket Detail
E1754 − 17a
FIG. 2 Sample Cylinder Assembly
5.2.1 Hastelloy C and 316 Stainless Steel Stock, suitable for 5.5.8 Hygrometer, capable of measuring moisture as low as
machining. 5 mg/kg (ppm) in glove bag or dry box.
5.2.2 Silver Chloride Windows, 0.5 by 2.5 cm.
5.6 Silicone Rubber Septa.
5.2.3 Perfluoroelastomer Sheet, 0.030 in. thickness.
5.7 Mechanical Shaker.
1 1
5.3 BallValves,Monel ⁄4in.valvewithpipeand ⁄4in.tube
5.8 Drying Oven.
ends.
6. Reagents
5.4 Needle Valves, nickel or Monel 6.35 mm ( ⁄4 in.) valve
with pipe and 6.35 mm ( ⁄4 in.) tube ends.
6.1 Purity of Water—See Specification D1193.
5.5 Sample Cylinder Assembly (see Fig. 2), consisting of:
6.2 Chlorine, liquid with less than 5 mg/kg (ppm) water.
5.5.1 Sample Cylinder, nickel, Monel, or tantalum; 400 to
6.3 Methylene Chloride (CH Cl ).
2 2
1000 mL capacity, double-ended, with valves at each end,
specially cleaned. Cylinders with both valves at one end and NOTE 2—This reagent is used for cooling purposes only.
withadiptubeononevalvehavebeenfoundtobesatisfactory.
6.4 Dry Ice (CO ).
Another option is to construct special cylinders containing a
6.5 Dry Nitrogen, (<5 mg/kg (ppm) water) to purge glove
septum fitting on one end.
bag or dry box and test equipment.
NOTE 1—A procedure for cleaning cylinders and valves, for use with
7. Hazards
liquid chlorine, is given in Test Method E806, Appendix X2.
5.5.2 Needle and Ball Valve, nickel body, having packing 7.1 Safety Precautions:
resistant to liquid chlorine. If nickel valves are not available, 7.1.1 Chlorine is a corrosive and toxic material. A well-
ventilated fume hood should be used to house all test
Monel valves may be used.
5.5.3 Septum, inserted into a 6.35 mm ( ⁄4 in.) nut. equipment, except the infrared spectrophotometer, when this
material is analyzed in the laboratory.
5.5.4 Glove Bag or Dry Box, purged with dry nitrogen (less
than 5 ppm water vapor). 7.1.2 Theanalysisshouldbeattemptedonlybypersonswho
are thoroughly familiar with the handling of chlorine, and even
5.5.5 Fittings, for transferring chlorine from one cylinder to
another. anexperiencedpersonshouldnotworkalone.Theanalystmust
be provided with adequate eye protection (chemical goggles
5.5.6 0to10- µL Syringe and 0 to 25-µL Syringe, 26-gage
needle. are recommended) and an approved chlorine respirator.
5.5.7 Dewar Flask, of sufficient size to hold a cylinder Splashes of liquid chlorine destroy clothing and if such
surrounded by dry ice and methylene chloride. The Dewar clothing is next to the skin, will produce irritation and burns.
flask should be supported by a wooden holder for safety 7.1.3 When sampling and working with chlorine out of
purposes. doors, people downwind from such operations should be
warned of the possible release of chlorine.
7.1.4 Itisrecommendedthatmeansbeavailablefordisposal
Monel is a registered trademark of Special Metals Corporation. of excess chlorine in an environmentally safe and acceptable
E1754 − 17a
manner. If chlorine cannot be disposed of in a chlorine weigh to the nearest gram, record, and label as No. 1. Once it
consuming process, a chlorine absorption system should be contains chlorine, it will be used to purge the infrared cell
provided.When the analysis and sampling regimen requires an beforestandardsareloaded.Usecapsonallvalves.Ifdiptubes
initialpurgingofchlorinefromacontainer,thepurgedchlorine are used, attach the dip tube to the needle valve. Check the
should be similarly handled. Purging to the atmosphere should hygrometer to make sure the atmosphere in the glove bag or
be avoided. dry box contains <5 mg/kg (ppm) moisture before performing
7.1.5 In the event chlorine is inhaled, first aid should be any transfers of chlorine.
summoned immediately.
9.2 Load the four cylinders with liquid chlorine. The liquid
chlorine should contain less than 5 mg/kg (ppm) water. All
8. Sampling
cylinders must contain at least 75 % by volume liquid chlorine
8.1 Sampling points should also be chosen with care.
(less than 25 % vapor space).All cylinders should be weighed
Ensure that the sample point is associated with flowing
to the nearest gram and recorded to determine the weight of
chlorine, and is not near a“ dead leg” where the concentrations
chlorine in each cylinder (Note 3). Place the filled cylinders
of impurities in the chlorine will never change because the
into the glove bag or dry box inside the hood. Place all fittings,
chlorine never moves. If sampling through secondary piping,
tools and equipment, including the purged infrared cell, in the
that piping should be purged well with nitrogen or dry air
glove bag or dry box. Wait until the hygrometer in the glove
before being blocked in. Otherwise, temperature variations can
bag or dry box is reading <5 mg/kg (ppm) moisture before
result in water vapor condensing inside the piping to contami-
proceeding.
nate the chlorine sample when it is grabbed. Finally, sampling
9.3 Remove the cap on ValveAof Cylinder No. 1 and blow
should be done at a sample point representative of the chlorine
with N to remove any trapped moisture. Do this each time a
needing to be analyzed.
connection is made. Then connect the cylinder and the special
8.1.1 Sampling from tank cars, barges, storage tanks, and
infrared cell to the filling apparatus (see Fig. 2) in such a way
large cylinders presents unique problems. Each facility,
that the liquid chlorine will flow into the cell and that the
however, must be capable of delivering a liquid sample (not
valvesonallpartsoftheapparatusareclosedpriortofillingthe
gas). See Chlorine Institute Pamphlet No. 1, “Chlorine
5 cell. For the following operations, refer to 7.1.4 on venting
Basics.” (See 49 CFR 173, including Parts 173.304, 173.314,
chlorine.
and 173.315.)
9.4 Open Valve F and then Valve A. Flush the filling
8.2 It is recommended that samples be collected from these
apparatus by partially opening Valve B for a few seconds and
facilities in the sample cylinder assembly listed in 5.5. Proper
then closing it. Leave Valve A open.
and safe sampling techniques must be followed. The cylinder
9.4.1 Open Valves E and C. Flush the cell by partially
must contain at least 75 % by volume of liquid chlorine (less
opening Valve D and observing flow, then close Valve C and
than 25 % vapor space).
then Valve D.
NOTE 3—Do not allow the cylinder to become liquid full. Tare the
9.5 FilltheinfraredcellbyopeningValveCandobservethe
cylinder, fill with water, and re-weigh to determine the weight of water in
the cylinder. Multiply this weight by 1.56 (the assumed specific gravity of
filling of the cell windows. Close Valve C and empty the cell
liquid chlorine) and by 0.75 to obtain the weight of chlorine to fill the
by opening Valve D. Close Valve D.
cylinder 75 % full. Example: The cylinder holds 1000 g of water (1000
mL, assuming a specific gravity of 1.0).The filled cylinder will hold 1560 9.6 Fill and empty the cell once more, as above.
g of chlorine, and at 75 % of capacity, it will contain 1170 g of chlorine.
9.6.1 Close Valve A and open Valve B, to purge the filling
8.3 The sample cylinders should be thoroughly dried by apparatus, then close.
placing in an oven at 105°C for at least6hor preferably
9.7 Remove the cylinder. Connect Cylinder No. 2 to the
overnight; the dip tubes are not heated, place them in a
filling apparatus after blowingValveAwith N . Make sure that
desiccator. Valves are also placed in the oven, but not as a part
thecylinderisconnectedtotheapparatusinsuchawaythatthe
of the cylinder (packings are resistant to this temperature).
liquid chlorine will flow into the cell and that the valves on all
After this treatment, the cylinders are cooled with plant air or
parts of the apparatus are closed prior to attempting to fill the
N having <5 mg/kg (ppm) moisture. The valves are removed,
cell. For the following operations, refer to 7.1.4 on venting
placed in a desiccator with a suitable drying agent, and cooled
chlorine. Repeat 9.4 to 9.6.
to room temperature.
9.8 Fill the cell by opening Valve C. Close Valve C and
9. Preparation of Standards for Calibration
invertthecelltoensurecompletefillingofthecellwindowand
then close Valve A.
9.1 Obtain four clean, evacuated sample cylinders. Only
cylinders that have been properly pressure-tested should be
9.9 Vent the residual chlorine from the filling apparatus by
used. Equip three with a ball valve and a needle valve, label
opening Valve B and then open Valve C a little and dump a
these Cylinders No. 2 through No. 4 and record weight to the
small amount of chlorine from the inverted cell, then quickly
nearestgram.Equipthefourthcylinderwithtwoneedlevalves,
close.Thecellwindowshouldhaveabout ⁄5vaporspacewhen
inverted. Then close Valves B and E.
9.10 Allow the cell to come to ambient temperature. Before
Available from The Chlorine Institute, Inc., 1300 Wilson Blvd., Suite 525,
Arlington, VA 22209. removing the cell from the filling apparatus, check again for
E1754 − 17a
adequate vapor space in the inverted cell window. If no vapor 9.19 Calculate the added concentration of water as milli-
space is seen, open Valve B and quickly open and close Valve grams per kilogram (parts per million) in the spiked standard.
C a little to dump some more chlorine. Make sure that no more
9.20 Spike Cylinders Nos. 3 and 4 with approximately the
1 1
than ⁄4 to ⁄5 of the cell window is vapor space when the cell
same amount of water for re
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM 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: E1754 − 17 E1754 − 17a
Standard Test Method for
Determination of Low Levels of Water in Liquid Chlorine By
Infrared Spectrophotometry
This standard is issued under the fixed designation E1754; 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*
1.1 This test method covers the determination of the content of water in liquid chlorine in the concentration range of 0.5 to 15
mg/kg (ppm).
1.2 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.
1.3 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety
precautions.
1.4 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. See Section 7 for specific hazards statements.
1.4 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety
precautions.
1.5 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.
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water
D6809 Guide for Quality Control and Quality Assurance Procedures for Aromatic Hydrocarbons and Related Materials
E806 Test Method for Carbon Tetrachloride and Chloroform in Liquid Chlorine by Direct Injection (Gas Chromatographic
Procedure)
2.2 Federal Standards:
49 CFR 173 Code of Federal Regulations Title 49 Transportation: Shippers’ General Requirements for Shipments and
Packaging, including Sections:
173.304 Charging of Cylinders with Liquefied Compressed Gas
173.314 Requirements for Compressed Gases in Tank Cars
173.315 Compressed Gases in Cargo Tanks and Portable Tank Containers
3. Summary of Test Method
3.1 A sample of liquid chlorine is introduced into a special infrared cell and maintained as a liquid under its own pressure. A
spectrometer scans from 400 to 4400 wavenumbers of the infrared transmission spectrum of liquid chlorine. This spectrum is then
ratioed to one obtained of the nitrogen-filled infrared cell previously. The ratioed spectrum is converted to absorbance, and the net
absorbance of the water band at 1596 wavenumbers, relative to a reference at 1663 wavenumbers, is determined. The amount of
water corresponding to this net absorbance is determined from a calibration curve prepared from the infrared absorbances of
standards that contain known concentrations of water in liquid chlorine.
This test method is under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons Aromatic, Industrial, Specialty and Related Chemicals and is the direct
responsibility of Subcommittee D16.16 on Industrial and Specialty Product Standards.
Current edition approved March 1, 2017July 1, 2017. Published March 2017July 2017. Originally approved in 1995. Last previous edition approved in 20082017 as E1754
– 08.17. DOI: 10.1520/E1754-17.10.1520/E1754-17a.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Available from U.S. Government Printing Office, Superintendent of Documents, 732 N. Capitol St., NW, Washington, DC 20401-0001, http://www.access.gpo.gov.
*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
E1754 − 17a
4. Significance and Use
4.1 Trace amounts of water may be detrimental to the use of chlorine in some applications. The amount of water in the chlorine
must be known to prevent problems during its use.
E1754 − 17a
5. Apparatus
5.1 Infrared Spectrometer, capable of measurements in the 1600 wavenumber region. An FTIR with 4 wavenumber resolution
is the instrument of choice, but dispersive instruments may also be used to achieve similar results.
5.2 Special Infrared Cell (see Fig. 1), neither cell size nor pathlength are critical to the analysis, but sensitivity and limit of
detection are dependent on pathlength. The concentration range reported in the scope is achievable with a 60-mm pathlength cell
constructed with:
NOTE 1—Drawing not to scale.
FIG. 1 Infrared Cell
E1754 − 17a
FIG. 1(a) Pipe Adapter
FIG. 1(b) Air Cap Detail
E1754 − 17a
FIG. 1(c) Body Detail
FIG. 1(d) Gasket Detail
E1754 − 17a
FIG. 1(e) Insert Detail
FIG. 1(f) Flange Detail
E1754 − 17a
FIG. 2 Sample Cylinder Assembly
5.2.1 Hastelloy C and 316 Stainless Steel Stock, suitable for machining.
FIG. 1(a) Pipe Adapter
E1754 − 17a
FIG. 1(b) Air Cap Detail
FIG. 1(c) Body Detail
E1754 − 17a
FIG. 1(d) Gasket Detail
FIG. 1(e) Insert Detail
FIG. 1(f) Flange Detail
E1754 − 17a
5.2.2 Silver Chloride Windows, 0.5 by 2.5 cm.
5.2.3 Perfluoroelastomer Sheet, 0.030 in. thickness.
1 1
5.3 Ball Valves, Monel ⁄4 in. valve with pipe and ⁄4 in. tube ends.
1 1
5.4 Needle Valves, nickel or Monel 6.35 mm ( ⁄4 in.) valve with pipe and 6.35 mm ( ⁄4 in.) tube ends.
5.5 Sample Cylinder Assembly (see Fig. 2), consisting of:
5.5.1 Sample Cylinder, nickel, Monel, or tantalum; 400 to 1000 mL capacity, double-ended, with valves at each end, specially
cleaned. Cylinders with both valves at one end and with a dip tube on one valve have been found to be satisfactory. Another option
is to construct special cylinders containing a septum fitting on one end.
NOTE 1—A procedure for cleaning cylinders and valves, for use with liquid chlorine, is given in Test Method E806, Appendix X2.
5.5.2 Needle and Ball Valve, nickel body, having packing resistant to liquid chlorine. If nickel valves are not available, Monel
valves may be used.
5.5.3 Septum, inserted into a 6.35 mm ( ⁄4 in.) nut.
5.5.4 Glove Bag or Dry Box, purged with dry nitrogen (less than 5 ppm water vapor).
5.5.5 Fittings, for transferring chlorine from one cylinder to another.
5.5.6 0 to 10- μL Syringe and 0 to 25-μL Syringe, 26-gage needle.
5.5.7 Dewar Flask, of sufficient size to hold a cylinder surrounded by dry ice and methylene chloride. The Dewar flask should
be supported by a wooden holder for safety purposes.
5.5.8 Hygrometer, capable of measuring moisture as low as 5 mg/kg (ppm) in glove bag or dry box.
5.6 Silicone Rubber Septa.
5.7 Mechanical Shaker.
5.8 Drying Oven.
6. Reagents
6.1 Purity of Water—See Specification D1193.
6.2 Chlorine, liquid with less than 5 mg/kg (ppm) water.
6.3 Methylene Chloride (CH Cl ).
2 2
NOTE 2—This reagent is used for cooling purposes only.
6.4 Dry Ice (CO ).
6.5 Dry Nitrogen, (<5 mg/kg (ppm) water) to purge glove bag or dry box and test equipment.
7. Hazards
7.1 Safety Precautions:
7.1.1 Chlorine is a corrosive and toxic material. A well-ventilated fume hood should be used to house all test equipment, except
the infrared spectrophotometer, when this material is analyzed in the laboratory.
7.1.2 The analysis should be attempted only by persons who are thoroughly familiar with the handling of chlorine, and even
an experienced person should not work alone. The analyst must be provided with adequate eye protection (chemical goggles are
recommended) and an approved chlorine respirator. Splashes of liquid chlorine destroy clothing and if such clothing is next to the
skin, will produce irritation and burns.
7.1.3 When sampling and working with chlorine out of doors, people downwind from such operations should be warned of the
possible release of chlorine.
7.1.4 It is recommended that means be available for disposal of excess chlorine in an environmentally safe and acceptable
manner. If chlorine cannot be disposed of in a chlorine consuming process, a chlorine absorption system should be provided. When
the analysis and sampling regimen requires an initial purging of chlorine from a container, the purged chlorine should be similarly
handled. Purging to the atmosphere should be avoided.
7.1.5 In the event chlorine is inhaled, first aid should be summoned immediately.
8. Sampling
8.1 Sampling points should also be chosen with care. Ensure that the sample point is associated with flowing chlorine, and is
not near a“ dead leg” where the concentrations of impurities in the chlorine will never change because the chlorine never moves.
If sampling through secondary piping, that piping should be purged well with nitrogen or dry air before being blocked in.
Monel is a registered trademark of Special Metals Corporation.
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Otherwise, temperature variations can result in water vapor condensing inside the piping to contaminate the chlorine sample when
it is grabbed. Finally, sampling should be done at a sample point representative of the chlorine needing to be analyzed.
8.1.1 Sampling from tank cars, barges, storage tanks, and large cylinders presents unique problems. Each facility, however, must
be capable of delivering a liquid sample (not gas). See Chlorine Institute Pamphlet No. 1, “Chlorine Basics.” (See 49 CFR 173,
including Parts 173.304, 173.314, and 173.315.)
8.2 It is recommended that samples be collected from these facilities in the sample cylinder assembly listed in 5.5. Proper and
safe sampling techniques must be followed. The cylinder must contain at least 75 % by volume of liquid chlorine (less than 25 %
vapor space).
NOTE 3—Do not allow the cylinder to become liquid full. Tare the cylinder, fill with water, and re-weigh to determine the weight of water in the
cylinder. Multiply this weight by 1.56 (the assumed specific gravity of liquid chlorine) and by 0.75 to obtain the weight of chlorine to fill the cylinder
75 % full. Example: The cylinder holds 1000 g of water (1000 mL, assuming a specific gravity of 1.0). The filled cylinder will hold 1560 g of chlorine,
and at 75 % of capacity, it will contain 1170 g of chlorine.
8.3 The sample cylinders should be thoroughly dried by placing in an oven at 105°C for at least 6 h or preferably overnight;
the dip tubes are not heated, place them in a desiccator. Valves are also placed in the oven, but not as a part of the cylinder (packings
are resistant to this temperature). After this treatment, the cylinders are cooled with plant air or N having <5 mg/kg (ppm)
moisture. The valves are removed, placed in a desiccator with a suitable drying agent, and cooled to room temperature.
9. Preparation of Standards for Calibration
9.1 Obtain four clean, evacuated sample cylinders. Only cylinders that have been properly pressure-tested should be used. Equip
three with a ball valve and a needle valve, label these Cylinders No. 2 through No. 4 and record weight to the nearest gram. Equip
the fourth cylinder with two needle valves, weigh to the nearest gram, record, and label as No. 1. Once it contains chlorine, it will
be used to purge the infrared cell before standards are loaded. Use caps on all valves. If dip tubes are used, attach the dip tube
to the needle valve. Check the hygrometer to make sure the atmosphere in the glove bag or dry box contains <5 mg/kg (ppm)
moisture before performing any transfers of chlorine.
9.2 Load the four cylinders with liquid chlorine. The liquid chlorine should contain less than 5 mg/kg (ppm) water. All cylinders
must contain at least 75 % by volume liquid chlorine (less than 25 % vapor space). All cylinders should be weighed to the nearest
gram and recorded to determine the weight of chlorine in each cylinder (Note 3). Place the filled cylinders into the glove bag or
dry box inside the hood. Place all fittings, tools and equipment, including the purged infrared cell, in the glove bag or dry box.
Wait until the hygrometer in the glove bag or dry box is reading <5 mg/kg (ppm) moisture before proceeding.
9.3 Remove the cap on Valve A of Cylinder No. 1 and blow with N to remove any trapped moisture. Do this each time a
connection is made. Then connect the cylinder and the special infrared cell to the filling apparatus (see Fig. 2) in such a way that
the liquid chlorine will flow into the cell and that the valves on all parts of the apparatus are closed prior to filling the cell. For
the following operations, refer to 7.1.4 on venting chlorine.
9.4 Open Valve F and then Valve A. Flush the filling apparatus by partially opening Valve B for a few seconds and then closing
it. Leave Valve A open.
9.4.1 Open Valves E and C. Flush the cell by partially opening Valve D and observing flow, then close Valve C and then Valve
D.
9.5 Fill the infrared cell by opening Valve C and observe the filling of the cell windows. Close Valve C and empty the cell by
opening Valve D. Close Valve D.
9.6 Fill and empty the cell once more, as above.
9.6.1 Close Valve A and open Valve B, to purge the filling apparatus, then close.
9.7 Remove the cylinder. Connect Cylinder No. 2 to the filling apparatus after blowing Valve A with N . Make sure that the
cylinder is connected to the apparatus in such a way that the liquid chlorine will flow into the cell and that the valves on all parts
of the apparatus are closed prior to attempting to fill the cell. For the following operations, refer to 7.1.4 on venting chlorine. Repeat
9.4 to 9.6.
9.8 Fill the cell by opening Valve C. Close Valve C and invert the cell to ensure complete filling of the cell window and then
close Valve A.
9.9 Vent the residual chlorine from the filling apparatus by opening Valve B and then open Valve C a little and dump a small
amount of chlorine from the inverted cell, then quickly close. The cell window should have about ⁄5 vapor space when inverted.
Then close Valves B and E.
9.10 Allow the cell to come to ambient temperature. Before removing the cell from the filling apparatus, check again for
adequate vapor space in the inverted cell window. If no vapor space is seen, open Valve B and quickly open and close Valve C
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