ASTM C1204-14

Standard Test Method for Uranium in Presence of Plutonium by Iron(II) Reduction in Phosphoric Acid Followed by Chromium(VI) Titration

SIGNIFICANCE AND USE
4.1 Factors governing selection of a method for the determination of uranium include available quantity of sample, sample purity, desired level of reliability, and equipment availability.  
4.2 This test method is suitable for samples between 20 to 300 mg of uranium, is applicable to fast breeder reactor (FBR)-mixed oxides having a uranium to plutonium ratio of 2.5 and greater, is tolerant towards most metallic impurity elements usually specified for FBR-mixed oxide fuel, and uses no special equipment.  
4.3 The ruggedness of the titration method has been studied for both the volumetric (6) and the weight (7) titration of uranium with dichromate.
SCOPE
1.1 This test method covers unirradiated uranium-plutonium mixed oxide having a uranium to plutonium ratio of 2.5 and greater. The presence of larger amounts of plutonium (Pu) that give lower uranium to plutonium ratios may give low analysis results for uranium (U) (1)2, if the amount of plutonium together with the uranium is sufficient to slow the reduction step and prevent complete reduction of the uranium in the allotted time. Use of this test method for lower uranium to plutonium ratios may be possible, especially when 20 to 50 mg quantities of uranium are being titrated rather than the 100 to 300 mg in the study cited in Ref (1). Confirmation of that information should be obtained before this test method is used for ratios of uranium to plutonium less than 2.5.  
1.2 The amount of uranium determined in the data presented in Section 12 was 20 to 50 mg. However, this test method, as stated, contains iron in excess of that needed to reduce the combined quantities of uranium and plutonium in a solution containing 300 mg of uranium with uranium to plutonium ratios greater than or equal to 2.5. Solutions containing up to 300 mg uranium with uranium to plutonium ratios greater than or equal to 2.5 have been analyzed (1) using the reagent volumes and conditions as described in Section 10.  
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 hazard statements, see Section 8.

General Information

• Status: Historical
• Publication Date: 31-May-2014
• ICS: 27.120.30 - Fissile materials and nuclear fuel technology
• Technical Committee: C26 - Nuclear Fuel Cycle
• Drafting Committee: C26.05 - Methods of Test

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
Designation: C1204 − 14
Standard Test Method for
Uranium in Presence of Plutonium by Iron(II) Reduction in
1
Phosphoric Acid Followed by Chromium(VI) Titration
This standard is issued under the fixed designation C1204; 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. Referenced Documents
3
2.1 ASTM Standards:
1.1 Thistestmethodcoversunirradiateduranium-plutonium
C852Guide for Design Criteria for Plutonium Gloveboxes
mixed oxide having a uranium to plutonium ratio of 2.5 and
C1128Guide for Preparation of Working Reference Materi-
greater. The presence of larger amounts of plutonium (Pu) that
als for Use in Analysis of Nuclear Fuel Cycle Materials
give lower uranium to plutonium ratios may give low analysis
2
C1168PracticeforPreparationandDissolutionofPlutonium
results for uranium (U) (1) , if the amount of plutonium
Materials for Analysis
together with the uranium is sufficient to slow the reduction
step and prevent complete reduction of the uranium in the
3. Summary of Test Method
allotted time. Use of this test method for lower uranium to
3.1 Samples are prepared by dissolution techniques detailed
plutoniumratiosmaybepossible,especiallywhen20to50mg
in Practice C1168 and Ref (2).Aliquants containing 20 to 300
quantities of uranium are being titrated rather than the 100 to
mg of uranium, as selected by the facility procedure, are
300 mg in the study cited in Ref (1). Confirmation of that
prepared by weight. The sample is fumed to incipient dryness
information should be obtained before this test method is used
after the addition of sulfuric acid. The sample is dissolved in
for ratios of uranium to plutonium less than 2.5.
dilute sulfuric acid prior to titration.
1.2 Theamountofuraniumdeterminedinthedatapresented
3.2 Uranium is reduced to uranium(IV) by excess ferrous
in Section 12 was 20 to 50 mg. However, this test method, as
(iron(II)) in concentrated phosphoric acid (H PO ) containing
3 4
stated, contains iron in excess of that needed to reduce the
sulfamic acid. The excess iron(II) is selectively oxidized by
combined quantities of uranium and plutonium in a solution
nitric acid (HNO ) in the presence of molybdenum(VI) cata-
3
containing 300 mg of uranium with uranium to plutonium
lyst. After the addition of vanadium(IV), the uranium(IV) is
ratios greater than or equal to 2.5. Solutions containing up to
titratedwithchromium(VI)toapotentiometricendpoint (3, 4).
300 mg uranium with uranium to plutonium ratios greater than
3.3 A single chromium(VI) titrant delivered manually on a
or equal to 2.5 have been analyzed (1) using the reagent
weight or volume basis is used. The concentration of the
volumes and conditions as described in Section 10.
chromium(VI) solution is dependent upon the amount of
1.3 The values stated in SI units are to be regarded as
uranium being titrated (see 7.8).Automated titrators that have
standard. No other units of measurement are included in this
comparable precisions can be used.
standard.
NOTE 1—An alternative ceric (V) sulfate or nitrate titrant may also be
1.4 This standard does not purport to address all of the
used, providing that the user demonstrates equivalent performance to the
safety concerns, if any, associated with its use. It is the dichromate titrant.
responsibility of the user of this standard to establish appro-
3.4 For the titration of uranium alone, the precision of the
priate safety and health practices and determine the applica-
modified Davies and Gray titration method has been signifi-
bility of regulatory limitations prior to use. For specific hazard
cantly improved by increasing the amount of uranium titrated
statements, see Section 8.
to 1 g and delivering about 90% of the titrant on a solid mass
basis followed by titration to the end point with a dilute titrant
(5). This modification has not been studied for the titration of
1
uranium in the presence of plutonium, and confirmation of its
ThistestmethodisunderthejurisdictionofASTMCommitteeC26onNuclear
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
applicability should be obtained by the facility prior to its use.
Test.
CurrenteditionapprovedJune1,2014.PublishedJuly2014.Originallyapproved
ε1
3
in 1991. Last previous edition approved in 2008 as C1204–02 (2008) . DOI: For referenced ASTM standards, visit the ASTM website, www.astm.org, or
10.1520/C1204-14. contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
2
Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof Standards volume information, refer to the standard’s Document Summary
...

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.
´1
Designation: C1204 − 02 (Reapproved 2008) C1204 − 14
Standard Test Method for
Uranium in Presence of Plutonium by Iron(II) Reduction in
1
Phosphoric Acid Followed by Chromium(VI) Titration
This standard is issued under the fixed designation C1204; 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
ε NOTE—Editorial changes were made throughout in July 2008.
1. Scope
1.1 This test method covers unirradiated uranium-plutonium mixed oxide having a uranium to plutonium ratio of 2.5 and
greater. The presence of larger amounts of plutonium (Pu) that give lower uranium to plutonium ratios may give low analysis
2
results for uranium (U) (1) , if the amount of plutonium together with the uranium is sufficient to slow the reduction step and
prevent complete reduction of the uranium in the allotted time. Use of this test method for lower uranium to plutonium ratios may
be possible, especially when 20 to 50 mg quantities of uranium are being titrated rather than the 100 to 300 mg in the study cited
in Ref (1). Confirmation of that information should be obtained before this test method is used for ratios of uranium to plutonium
less than 2.5.
1.2 The amount of uranium determined in the data presented in Section 12 was 20 to 50 mg. However, this test method, as
stated, contains iron in excess of that needed to reduce the combined quantities of uranium and plutonium in a solution containing
300 mg of uranium with uranium to plutonium ratios greater than or equal to 2.5. Solutions containing up to 300 mg uranium with
uranium to plutonium ratios greater than or equal to 2.5 have been analyzed (1) using the reagent volumes and conditions as
described in Section 10.
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 hazard statements, see Section 8.
2. Referenced Documents
3
2.1 ASTM Standards:
C852 Guide for Design Criteria for Plutonium Gloveboxes
C1128 Guide for Preparation of Working Reference Materials for Use in Analysis of Nuclear Fuel Cycle Materials
C1168 Practice for Preparation and Dissolution of Plutonium Materials for Analysis
3. Summary of Test Method
3.1 Samples are prepared by dissolution techniques detailed in Practice C1168 and Ref (2). Aliquants containing 20 to 300 mg
of uranium, as selected by the facility procedure, are prepared by weight. The sample is fumed to incipient dryness after the
addition of sulfuric acid. The sample is dissolved in dilute sulfuric acid prior to titration.
3.2 Uranium is reduced to uranium(IV) by excess ferrous (iron(II)) in concentrated phosphoric acid (H PO ) containing
3 4
sulfamic acid. The excess iron(II) is selectively oxidized by nitric acid (HNO ) in the presence of molybdenum(VI) catalyst. After
3
the addition of vanadium(IV), the uranium(IV) is titrated with chromium(VI) to a potentiometric end point (3, 4).
3.3 A single chromium(VI) titrant delivered manually on a weight or volume basis is used. The concentration of the
chromium(VI) solution is dependent upon the amount of uranium being titrated (see 7.8). Automated titrators that have comparable
precisions can be used.
1
This test method is under the jurisdiction of ASTM Committee C26 on Nuclear Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of Test.
Current edition approved June 1, 2008June 1, 2014. Published July 2008July 2014. Originally approved in 1991. Last previous edition approved in 20022008 as
ε1
C1204 – 02.C1204 – 02 (2008) . DOI: 10.1520/C1204-02R08E01.10.1520/C1204-14.
2
The boldface numbers in parentheses refer to the list of references at the end of this test method.
3
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.
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