ASTM D1385-07(2013)e1
(Test Method)Standard Test Method for Hydrazine in Water
Standard Test Method for Hydrazine in Water
SIGNIFICANCE AND USE
5.1 Hydrazine is a man-made chemical and is not found in natural waters. The determination of hydrazine is usually made on boiler feedwaters, process waters, and other waters that have been treated with hydrazine (N2H4) for the purpose of maintaining residuals to prevent corrosion by dissolved oxygen. This reducing chemical reacts with dissolved oxygen to form nitrogen and water. However, under certain conditions it can also decompose to form ammonia and nitrogen. Hydrazine is used extensively as a preboiler treatment chemical for high-pressure boilers to scavenge small amounts of dissolved oxygen that are not removed by mechanical aeration. It has the advantage over sulfite treatment in that it does not produce any dissolved solids in the boiler water. Hydrazine is often determined in concentrations below 0.1 mg/L. However, in layup solutions for the protection of idle boilers, hydrazine may be present in concentrations as high as 200 mg/L.
5.2 Additionally, hydrazine provides protection where reducing conditions are required, particularly in mixed metallurgy systems for the protection of the copper alloys.
5.3 Hydrazine is a suspected carcinogen and a threshold limit value in the atmosphere of 1.0 mg/L has been set by OSHA. When in an aqueous solution, hydrazine will oxidize to nitrogen and water in the presence of air over a relatively short period of time.
SCOPE
1.1 This test method covers2 the colorimetric determination of hydrazine in boiler feed waters, condensates, natural, and well waters that have been treated with hydrazine (N2H 4). This test method is usable in the range from 5.0 to 200 μg/L (ppb) hydrazine. The range is for photometric measurements made at 458 nm in 50 mm cell. Higher concentrations of hydrazine can also be determined by taking a more diluted sample.
1.2 It is the users' responsibility to ensure the validity of this test method for untested types of waters.
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 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. For specific precautionary statements, see 5.3, Note 1, and Footnote 8.
General Information
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Standards Content (Sample)
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
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Designation: D1385 − 07 (Reapproved 2013)
Standard Test Method for
Hydrazine in Water
This standard is issued under the fixed designation D1385; 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.
ε NOTE—This standard was reapproved with editorial changes in January 2013.
1. Scope D3370 Practices for Sampling Water from Closed Conduits
D5810 Guide for Spiking into Aqueous Samples
1.1 This test method covers the colorimetric determination
D5847 Practice for Writing Quality Control Specifications
of hydrazine in boiler feed waters, condensates, natural, and
for Standard Test Methods for Water Analysis
well waters that have been treated with hydrazine (N H ).This
2 4
E60 Practice for Analysis of Metals, Ores, and Related
test method is usable in the range from 5.0 to 200 µg/L (ppb)
Materials by Spectrophotometry
hydrazine.The range is for photometric measurements made at
E275 Practice for Describing and Measuring Performance of
458 nm in 50 mm cell. Higher concentrations of hydrazine can
Ultraviolet and Visible Spectrophotometers
also be determined by taking a more diluted sample.
1.2 Itistheusers’responsibilitytoensurethevalidityofthis
3. Terminology
test method for untested types of waters.
3.1 Definitions—For definitions of terms used in this test
1.3 The values stated in SI units are to be regarded as
method, refer to Terminology D1129.
standard. No other units of measurement are included in this
standard.
4. Summary of Test Method
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 4.1 When a solution of p-dimethylaminobenzaldehyde in
responsibility of the user of this standard to establish appro-
methyl alcohol and hydrochloric acid is added to hydrazine in
priate safety and health practices and determine the applica- dilutedhydrochloricacidsolution,acharacteristicyellowcolor
bility of regulatory limitations prior to use. For specific
of p-dimethylaminobenzalazine is formed. The yellow color
precautionary statements, see 5.3, Note 1, and Footnote 8.
formed is proportional to the hydrazine present and is in good
agreement with Beer’s law in the range from 5.0 to 200 µg/L
2. Referenced Documents
(ppb) hydrazine.
2.1 ASTM Standards:
D1066 Practice for Sampling Steam 5. Significance and Use
D1129 Terminology Relating to Water
5.1 Hydrazine is a man-made chemical and is not found in
D1193 Specification for Reagent Water
natural waters.The determination of hydrazine is usually made
on boiler feedwaters, process waters, and other waters that
have been treated with hydrazine (N H ) for the purpose of
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This test method is under the jurisdiction of ASTM Committee D19 on Water
maintaining residuals to prevent corrosion by dissolved oxy-
and is the responsibility of Subcommittee D19.03 on Sampling Water and
Water-Formed Deposits, Analysis of Water for Power Generation and Process Use,
gen. This reducing chemical reacts with dissolved oxygen to
On-Line Water Analysis, and Surveillance of Water
form nitrogen and water. However, under certain conditions it
Current edition approved Jan. 1, 2013. Published February 2013. Originally
can also decompose to form ammonia and nitrogen. Hydrazine
approved in 1967. Last previous edition approved in 2007 as D1385 – 07. DOI:
10.1520/D1385-07R13E01. is used extensively as a preboiler treatment chemical for
For further information on this test method, the following references may be of
high-pressure boilers to scavenge small amounts of dissolved
interest: Watt, G. W., and Chrisp, J. D., “Spectrophotometric Method for the
oxygen that are not removed by mechanical aeration. It has the
Determination of Hydrazine,” Analytical Chemistry, Vol 24, No. 12, 1952, pp.
advantage over sulfite treatment in that it does not produce any
2006–2008,andWood,P.R.,“DeterminationofMaleicHydrazideResiduesinPlant
and Animal Tissue,” Analytical Chemistry, Vol 25, No. 12, 1953, pp. 1879–1883.
dissolved solids in the boiler water. Hydrazine is often deter-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
mined in concentrations below 0.1 mg/L. However, in layup
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
solutions for the protection of idle boilers, hydrazine may be
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. present in concentrations as high as 200 mg/L.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D1385 − 07 (2013)
5.2 Additionally, hydrazine provides protection where re- 8.4 Hydrazine Solution, Standard(1.0mL=0.500µgN H )
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ducing conditions are required, particularly in mixed metal- —Dilute 5.0 mL of hydrazine stock solution to 1 L with water
lurgy systems for the protection of the copper alloys. and mix. Prepare as needed.
5.3 Hydrazine is a suspected carcinogen and a threshold
NOTE 1—Warning: Hydrazine is a suspected carcinogen and should be
handled with care.
limit value in the atmosphere of 1.0 mg/L has been set by
OSHA.When in an aqueous solution, hydrazine will oxidize to
8.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
nitrogen and water in the presence of air over a relatively short
chloric acid (HCl).
period of time.
8.6 p-Dimethylaminobenzaldehyde Solution—Dissolve 4.0
g of p-dimethylaminobenzaldehyde [(CH ) NC H CHO] in
6. Interferences 3 2 6 4
200 mL of methyl alcohol (CH OH) and 20 mL of HCl (sp gr
6.1 The substances normally present in industrial water do
1.19). Store in a dark bottle out of direct sunlight.
not interfere with the test; however, the hydrazine content may
be diminished by oxidizing agents, such as chlorine, bromine,
9. Sampling
and iodine, collected with the sample or absorbed by it prior to
9.1 Collect the sample in accordance with Practices D3370
testing.
or Practice D1066, whichever is applicable (Warning, see
6.2 Colors in the prescribed wavelengths also interfere, as
Note 1).
do other dark colors or turbidities that cannot be overcome.
9.2 Acidifyanddilutethesampleassoonastakenbyadding
6.3 Aromatic amines, such as aniline, will also interfere.
1 mLof concentrated HCl (sp gr 1.19) to a 100-mLvolumetric
flask and then pipetting 50 mLof the sample into the flask and
7. Apparatus
diluting to 100 mL. Prepare a blank with water at the same
7.1 Photometer—Aspectrophotometersuitableformeasure-
time.
ments at 458 nm and capable of holding cells with a light path
9.3 A smaller sample aliquot should be taken if the hydra-
of 50 mm should be used. Filter photometers and photometric
zine concentration is greater than 200 µg/L.
practices prescribed in this test method shall conform to
Practice E60, and spectrophotometers to Practice E275.
10. Calibration
7.2 Certain photoelectric filter photometers are capable of
10.1 Prepare a series of standard hydrazine solutions by
measurementat425nm,butnotat458nm.Measurementsmay
pipetting 0.0, 5.0, 10.0, 25.0, 50.0, 100.0, and 200.0 mL of
be made at 425 nm with a reduction in sensitivity of approxi-
hydrazine standard solution (1.0 mL = 0.500 µg N H ) into
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mately 50 % of that possible at 458 nm.
500-mL volumetric flasks. Add 5 mL of HCl (sp gr 1.19) to
7.3 Instrumentsthatreadoutindirectconcentrationcanalso
each flask and dilute with water to 500 mL and mix well. This
be used. Manufacturer’s instructions should be followed.
will give standard solutions containing 0, 5.0, 10.0, 25.0, 50.0,
100, and 200 µg/L (ppb) of hydrazine.
8. Reagents
10.2 Pipet 50.0-mL portions of the hydrazine standard
8.1 Purity of Reagents—Reagent grade chemicals shall be
solutions into clean, dry 100-mLbeakers or flasks and proceed
used in all tests. Unless otherwise indicated, it is intended that
as directed in 11.2. Plot absorbance on the ordinate and
all reagents shall conform to the specifications of the Commit-
micrograms per litre of hydrazine on the abscissa of linear
tee onAnalytical Reagents of theAmerican Chemical Society,
graph paper. Alternately, graph the data in an electronic
where such specifications are available. Other grades may be
spreadsheet or use an instrument that reads out in direct
used, provided it is first ascertained that the reagent is
concentrations.
sufficiently high in purity to permit its use without lessening
the accuracy of the determinations. 10.3 A separate calibration curve must be made for each
photometer and a recalibration must be made if it is necessary
8.2 Purity of Water—Unless otherwise indicated, references
to change the cell, lamp, or filter, or if any other alterations of
to water shall be understood to mean reagent water conforming
instrument or reagents are made. Check the curve for each
to the quantitative requirements of Type III reagent water in
series of tests by runni
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