ASTM C1502-01

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Designation:C1502–01
Standard Test Method for
Determination of Total Chlorine and Fluorine in Uranium
Dioxide and Gadolinium Oxide
This standard is issued under the fixed designation C 1502; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope 4. Significance and Use
1.1 This test method covers the determination of chlorine 4.1 The method is designed to show whether or not the
and fluorine in nuclear-grade uranium dioxide (UO ) powder tested materials meet the specifications as given in either
and pellets, nuclear grade gadolinium oxide (Gd O ) powder Specification C 753, C 776, C 888 or C 922.
2 3
and gadolinium oxide-uranium oxide (Gd O -UO ) powder
2 3 2
5. Interferences
and pellets.
5.1 The buffer controls the pH of the measured solution to
1.2 Witha2gramUO samplesizethedetectionlimitofthe
method is 4 µg/g for chlorine and 2 µg/g for fluorine. The avoid hydroxide ion interference or the formation of hydrogen
complexes with fluoride.
maximum concentration determined with a 2 gram sample is
500 µg/g for both chlorine and fluorine. The sample size used 5.2 Bromide, iodide, cyanide and sulfide, if present in the
condensate, interfere in the measurement of chloride with
in this test method can vary from 1 to 10 grams resulting in a
corresponding change in the detection limits and range. ion-selective electrodes, but have very little effect upon the
measurement of fluoride with ion-selective electrodes.
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the 5.3 As the ionic activity of the chloride and fluoride ions is
temperature dependent, the standard solutions and sample
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- solutions should be measured at the same temperature.
bility of regulatory limitations prior to use.
6. Apparatus
2. Referenced Documents
6.1 Pyrohydrolysis Equipment, the assembly of suitable
2.1 ASTM Standards: equipment is shown in Fig. 1.
6.2 Gas Flow Regulator and Flowmeter.
C 753 Specification for Nuclear-Grade, Sinterable Uranium
Dioxide Powder 6.3 Hot Plate, used to warm the water saturating the sparge
gas to 50–80°C.
C 776 Specification for Sintered Uranium Dioxide Pellets
C 888 Specification for Nuclear-Grade Gadolinium Oxide 6.4 Combustion Tube Furnace, having a bore of about 32
mm with a length of about 300 mm and the capability of
(Gd O ) Powder
2 3
C 922 Specification for Sintered Gadolinium Oxide— maintaining a temperature of 950 6 25°C. Combustion tube
furnaces with different dimensions may be satisfactory. Tem-
Uranium Dioxide Pellets
D 1193 Specification for Reagent Water peratures between 900 and 1000°C have been found to be
satisfactory.
3. Summary of Test Method
6.5 Quartz Reaction Tube (Fig. 2)—The exit end should not
3.1 The halogens are separated from the test materials by extend more than 50 mm beyond the furnace with a ground
pyrohydrolysis in a quartz tube with a stream of wet oxygen or joint connecting to the delivery tube.The delivery tube extends
air at a temperature of 900 to 1000°C. (1-4) Chloride and into a polyethylene or Pyrex absorption vessel with a tip
fluoride are volatilized simultaneously as acids, absorbed in a capable of giving a stream of very fine bubbles. A second
buffer solution as chloride and fluoride and measured with ion absorption vessel connected in series, may be necessary to
selective electrodes (4-6). ensure complete collection of the fluorine and chlorine from
the sample.
6.6 Combustion Boat, a ceramic, platinum or quartz boat
This test method is under the jurisdiction ofASTM Committee C26 on Nuclear
witha10mLcapacity(approx.90–100mmlong,13mmwide,
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of
and 10 mm high). Boats with different dimensions may be
Test.
Current edition approved June 10, 2001. Published September 2001.
satisfactory.
Annual Book of ASTM Standards, Vol 12.01.
Annual Book of ASTM Standards, Vol 11.01.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C1502
FIG. 1 Pyrohydrolysis Equipment
FIG. 2 Quartz Reaction Tube
6.7 Absorption Vessel, a 50-ml polyethylene graduate or Analytical Reagents of theAmerican Chemical Society, where
tube is satisfactory. such specifications are available. Other grades may be used,
6.8 Ion-Selective Electrodes,fluoride-selectiveactivityelec- provided it is first ascertained that the reagent is of sufficiently
4 5
trode , chloride-selective activity electrode . Combination high purity to permit its use without lessening the accuracy of
electrodes may be suitable. the determination.
6.9 Double-Junction Reference Electrode , such as a silver- 7.2 Accelerator—Two accelerators have been investigated
silver chloride with appropriate filling solutions. for this system, halogen free U O and a flux of sodium
3 8
6.10 pH/mV Meter—The meter should have minimum reso- tungstate and tungsten trioxide. (1, 2) Halogen free U O
3 8
lution of 1 mV. requires no special preparation before use but will require a
6.11 Magnetic Stirrer. longer pyrohydrolysis period. The flux of sodium tungstate
6.12 Beakers, 50 mL polyethylene. (Na WO ) with tungsten trioxide (WO ) may reduce the
2 4 3
pyrohydrolysis period by half but it requires the following
7. Reagents
special preparation. Dehydrate 165 g of Na WO in a large
2 4
7.1 Purity of Reagents—Reagent grade chemicals shall be platinum dish. Transfer the dried material to a mortar, add 116
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, D.C. For suggestions on the testing of reagents not
The Orion Model 9409 has been found satisfactory. listed by theAmerican Chemical Society, see Reagent Chemicals and Standards,by
The Orion Model 9617 has been found satisfactory. Joseph Rosin, D. Van Nostrand Company, Inc., New York, New York, and the
The Orion Model 9002 has been found satisfactory. United States Pharmacopeia.
C1502
gof WO , and grind the mixture to ensure good mixing. 8.5.6 Continue the reaction for 1 hour. Thirty minutes may
Transfer the mixture into a platinum dish and heat with a be sufficient with the tungstate flux.
burner for 2 h. Cool the melt, transfer the flux to a mortar and
NOTE 1—The time required to complete the pyrohydrolysis will vary
grind to a coarse powder. Store the flux in an airtight bottle.
with differences in accelerator type, equipment and sample type. To
Mix about8gofflux with each portion of sample to be
establish the total time required for complete pyrohydrolysis, replace the
pyrohydrolyzed.
buffer solution at 15 to 30 minute intervals and continue the reaction until
7.3 Buffer Solution (0.1 M)—Dissolve 10 g, potassium complete.
acetate (KC H O ) in water, add 5 mL of acetic acid
2 3 2
8.5.7 When the pyrohydrolysis is completed, transfer the
(CH CO H,spgr1.05),anddiluteto1L.Otherbuffersmaybe
3 2
buffer solution to a 25-mLvolumetric flask. Rinse the delivery
satisfactory. It will be necessary to validate the buffers and
tube (including inside) and collection tube with a minimum of
operating conditions with spike recovery determinations.
buffer solution. Make up to volume with buffer.
7.4 Chloride, Standard Solution (100 µg
...