a statistical review of the oxygen data from the gas .../67531/metadc706557/m2/1/high... · a...

WSRC-RP-99-O0595

A Statistical Review of the Oxygen Data from the Gas GenerationTests Supporting the Revision of the 9975 SARP

by

T. B. Edwards

Westinghouse Savannah River Company

Savannah River SiteAiken, South Carolina 29808

DOE Contract No. DE-AC09-96SR1 8500

This paper was prepared in connection with work done under the above contract number with the U. S.Department of Energy. By acceptance of this paper, the publisher ancf/or recipient acknowledges the U. S.Government’s right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper, alongwith the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper.

,

WSRC-RP-99-O0595Revision O

A STATISTICALREVIEWOFTHEOXYGENDATAFROMTHEGAS GENERATIONTESTSSUPPORTINGTHEREVISIONOFTHE9975SARP (U)

T. B. Edwards

@o NsmlljrpQ.%

●

Westinghouse Savannah River CompanySavannah River Technology CenterAiken, SC 29808

PREPARED FOR THE U.S. DEPARTMENT OF ENERGY UNDER CONTRACT NO. DE-AC09-96SR18500

>

WSRC-RP-99-O0595 ‘ ‘ ,Revision O

DISCLAIMER

This report was prepared as an account of work sponsored by an agency of the United StatesGovernment. Neither the UnitedStatesGovernmentnor any agency thereof, nor any of theiremployees, makes any warranty, express or impliedj or assumes any legal liability or responsibilityfor the accuracy, completeness, or usefidness of any information, apparatus, product or processdisclosed, or represents that its use would not infringe privately owned rights. Reference herein toany specific commercial product, process or service by trade name, trademark, manufacturer, orotherwise does not necessarily constitute or imply its endorsement, recommendation, or favoringby the United States Government or any agency thereof. The views and opinions of authorsexpressed herein do not necessarily state or reflect those of the United States Government or anyagency thereof.

This report has been reproduced directly from the best available copy.

Available for sale to the public, in paper, from: U.S. Department of Commerce, National TechnicalInformation Service, 52S5 Port Royal Road, Springfield, VA 22161, phone: (800) 553-6847fax: (703) 605-6900email: orders%tis.fedworld.govonline ordering: http:hvww.ntis.govlordering.htm

Available electronically at http:hvww.doe.govlbridgeAvaiIable for a processing fee to U.S. Department of Energy and its contractors, in paper, from:U.S. Department of Energy, Office of Scientific and Technical Information, P.O. Box 62, OakRidge, TN 37831-0062, phone: (865) 576-8401fax: (865) 576-5728email: reports @?adonis.osti.gov

DISCLAIMER

Portions of this document may be illegiblein electronic image products. Images areproduced from the best available originaldocument.

.


A STATISTICALREVIEWOFTHEOXYGENDATAFROMTHEGAS GENERATIONTESTSSUPPORTINGTHEREVISIONOFTHE9975SARP (U)

T. B. Edwards

July 15, 1999

T. B. Edwards, AuthorStatistical Consulting Section

J. H.v

e er, Technical Reviewer

Statisti Consulting Section

C. P. Holding-Smith~~agerEngineering Modeling & Simulation GroupAuthorized Derivative Classifier

4A-ADate

*

%%9-*

...111

.

WSRC-RP-99-O0595 “ ‘Revision O

This page intentionally left blank.

iv


IntrOdUCtiOnThe Chemical and Hydrogen Technology Section (CHT) of the Savannah RiverTechnology Center (SRTC) has conducted a series of gas generation tests insupport of the revision of the safety analysis report for packaging (SARP) for the9975 container, developed at the Savarinah River Site (SRS). The Packaging andTransportation Group of SRTC is coordinating the revision to this SARP. A TaskTechnical and Quality Assurance Plan directing this work was issued by CHT inFebruary 1999 [1].

Initially, the primary interest in this testing was hydrogen generation. From [1],these gas “generation tests can be tracked in real-time by measuring the pressureof a sealed container of the materials being studied. Because multiple gas phasereactions are produced in the radiation field of the sample, material pressuremeasurements do not necessarily define the quantity of H2 generated. However,the change in total molecules of gas can be calculated using the ideal gas lawfrom the pressure measurement, known container volume and sampletemperature. A measurement of the actual headspace gases must be completed tocalculate the H2 generation rate for a particular sample.”

As the results from these tests were reviewed, however, questions arose regardingthe oxygen in the headspace gases. Specifically, do the data from some testsindicate that oxygen was generated for those tests? And do the data for other testsindicate that the oxygen was depleted for them? A statistical analysis of theoxygen data derived from these tests is provided in this report to help answerthese questions.

This analysis was conducted using JMP@ Version 3.2.2, a commercial softwarepackage of the SAS Institute, Inc., in Cary, NC [2].

DISCUSSIONIn this section various plots of the oxygen data are reviewed; the tests are groupedinto similar types of experiments, which are then studied; measurement andanalytical uncertainties are propagated through the equations used to determinethe change in oxygen; and finally, the test results are judged for significant 02changes based upon their corresponding uncertainties. As part of this finalassessment, the results from those tests that are thought to be most representativeof the operational window for the 9975 package are summarized.

The data from these tests are provided in Table Al of the Appendix. A testidentifier is provided in the first column of this table. This identifier is usedthroughout this report to designate specific tests. Table A2 in the Appendixprovides additional information for these tests designated using these same testidentifying numbers.

/

WSRC-RP-99-O0595 ‘ ‘Revision O

.As described above for H2, the determination of interest for 02 is the change intotal 02 molecules from the beginning to the end of each test in the sample vessel.

This determination is made using the following equation

mPzV aPIVr=n2–nl= .—

RT2 RT1(1)

where nl is an estimate of the initial moles of 02 in the headspace gasescontainer and n2 is an estimate of the final moles of 02 in the headspace

of thegases.

Equation (1) also shows how these estimates are determined using the ideal gaslaw. In equation (l), the term “a” represents the initial 02 as a fraction of theheadspace gas volume, V (in cubic centimeters, cc), at an initial pressure of PI (intorr) and temperature of T1 (in degrees Kelvin, ‘K). R is the universal gas

torr. ccconstant, 62324.73 The “m” term in equation (1) represents the final

K. mole”02 concentration as a fraction of the headspace gases of volume Vat a pressure ofP2 (in torr) and temperature T2 (“K).

The value of “a” for each experiment is the fraction of 02 in air, for which thereference value is 0.20946. The value for “m” was determined by gaschromatography utilizing a sample of the headspace gases taken by syringe at theend of the test. These values along with results from equation (1) are provided inTable Al.

INITIAL LOOK AT THE OXYGEN DATAExhibit Al in the Appendix provides a plot of the initial 02 molar value versusthe corresponding final value by test. Some of those tests with final 02 valueslarger than their initial values are labeled with their test number in this plot.Exhibit A2 in the Appendix provides a plot of the change. in 02 (final minusinitial) by test number. A reference line at zero is also shown on this plot. Twoquestions of interest in this last plot are: “Which of these test results indicate asignificant increase in 02 (if any)?” and “Which of these tests indicate asignificant decrease in 02 (if any)?”

In order to answer these questions, an idea of the repeatability of the outcomesfrom similar tests must be determined. The test descriptions in Table A2 of theAppendix were used to group the tests into the categories indicated in Table 1.

Table 1: Types of TestsType Tests

Pu02 + MgO 1,11,23 H,25,26Pu02 + CaF 9, 14, 19

Pu Cake 17,44,50,52PU02 12,16 H,41,51

Pu02 + CaO 2,8, 15H3,4,5,6,7, 10, 13, 18,20,21,22,24,28,29, 30,31,32,

Other 33,34,35,36,37,38,39, 40,41,42,43,45,46,47, 48,49,53,54,55,56,57,58, 59

2

..WSRC-RP-99-O0595

Revision O

An “H” following a test number indicates that that particular test was heated,possibly differentiating it from the other tests in its group.

Exhibit A3 in the Appendix provides a look at the change in 02 by group type.Descriptive statistics for each of these groups are also provided in this exhibit.Note that the heated tests (those with the “H’ suffix in Table 1) are labeled (inaddition to those that were labeled earlier) in this exhibit and that they result in achange in 02 that appears to be different from their unheated counterparts. Theaverage and standard deviation of each group containing a heated test arecomputed including and excluding this test.

The repeatability of a test of the 9975 package maybe represented by the standarddeviation in the measurements of set of identical experiments. Each of the first 5groups from Table 1 (excluding the heated tests) is to be considered as a set ofnearly identical experiments. Their standard deviations range from 0.000071 to0.000002 moles of 02 with a pooled estimate of the standard deviation across allfive groups of 0.00004 moles. When considered on a percentage basis as arelative (to the mean 02 change) standard deviation, they range from about 21%to about 101% of the average 02 change for the group with a pooled relativestandard deviation of about 88% (using a one-way analysis of variance approach).In summary, a 2-sigma uncertainty determined from these results would be lead toa limit of +/- 0.00008 moles and +/- 176% of reading for absolute and relativeerrors, respectively. 1 Obviously, assessing the 02 changes using the relativeerrors leads to insignificant differences between the initial and final oxygen for allof the tests. For those tests showing a potential 02 increase, the absolute error 2-sigma limit leads to only 28, 48, and 49 being significant at an approximate 95%confidence level.

Part of the variation seen among the results for each of these groups is from,

measurement and analytical uncertainty and part is from differences in theconditions among each set of repeated tests (i.e., the conditions of the tests in eachgroup may not have been as “identical” as desired). The next section looks at thevariation due to the first of these two categories via the approach of errorpropagation. Before moving on to that topic, consider two additional looks atthese data.

The first is a plot of the 02 change versus headspace volume (in cc) across all ofthe tests, which is provided in Exhibit A4 in the Appendix. The volume ofheadspace gases in the container of each test is plotted along the x-axis. Alongthe y-axis the initial moles of 02 are plotted as a solid light-gray line. The finalmoles of 02 are also plotted on the y-axis, and their values are indicated by thesymbol “x”. While several of the tests showing a potential increase in 02 have aheadspace gas volume in the interval from 65 to 75 cc, other tests with volumes ofonly 30 cc also show a potential increase in 02. Thus, there is no obvious

1 Absolute and relative errors are discussed later in this section.

3

WSRC-RP-99-00595 ‘Revision O

relationship between the initial headspace gas volume and the generation ordepletion of 02.

One of the key steps in measuring the final 02 value is injecting a sample from theheadspace gas of the test container into a gas chromatography. The recovery ofthis sample as reflected by its total sample volume percent determination is acritical measurement in this procedure. The target value for this determination is100%. Exhibit A5 in the Appendix provides a plot of the 02 changes versus thetotal sample volume percent determinations for these tests. There is no obviousrelationship between the total sample volume percent determination and thegeneration or depletion of 02.

PROPAGATION OF MEASUREMENT UNCERTAINTIES

As evident in equation (l), the determination of r, the difference in moles of 02from the beginning to the end of a test, is dependent on several measurementsconducted over the course of the test. One question of interest as the results ofthese tests are evaluated is the potential impact of the uncertainties of thesemeasurements on the derived values for r. Propagating the measurementuncertainties or errors afflicting the terms of equation (1) into the resultant rreveals this potential impact.

The errors in experimental measurements fall into the two broad categories of biaserrors and random errors. Bias is related to accuracy, the closeness of agreementbetween the measured value and the true value.2 Randomness of a measurementis related to the precision or repeatability of the measurement. Appropriatelytaken together, these two errors yield the uncertainty of the measurement. Theerror propagation for equation (1) conducted here follows the framework providedin reference [3]. This reference also provides a full discussion of the practice ofand underlying theory for uncertainty analysis in an experimental setting. It is alinearized approach based on the use of a Taylor series expansion of equation ( 1).

Using the approach and terminology of [3], a 95’% coverage estimate of theuncertainty in the result r, Ur, can be expressed as

(2)

where Br represents the 95% confidence bound of the bias limit for r, Sr

represents the estimate of the standard deviation of the random errors, and t is thetwo-tailed, 95% Student t value (i.e., the 97.5th percentile, with degrees offreedom equal to those associated with the estimate of S, ).

2 In the situation where bias errors are known, the corresponding measurements are frequentlycorrected for these biases. Some random errors may been induced into the measurement by thisprocess, however. In addition, the durations of the biases often vary. Some bias or systematicerrors may remain constrmt over only a few measurements while others may afflict an entireexperimental study. For this study, the approach taken is to select bounding values (at a 95%confidence level) for the potentiaJ measurement biases.

4

,WSRC-RP-99-O0595

Revision O

The bias (B, ) and precision (S, ) errors for r are estimated by propagating the bias

( Bi ) and precision (Si ) errors of each measurement term i of equation (1) using a

Taylor’s series expansion as indicated in the following equations:

B: = ~O~B~ + 2J~’~ eiOjpijBiBji=l i=l j=i+l

and

(3)

(4)

where the summations are over the J (=7) terms of equation (1), which are listed

in Table 2 and which contribute uncertainty to the resultant r, each ei = &

represents the partial derivative of equation (1) with respect to the ith term of thatequation, each Bi represents the 95% confidence estimate of the bias for the ithsuch term, Si represents the standard deviation of the precision errors for this ithterm, the corresponding Student t value is chosen for 9570 (two-tailed) confidence

and reflecting the degrees of freedom associated with Si, the pij expression

represents the correlation between the biases for terms i and j, and the pi;

expression represents the correlation between the random errors for terms i and j.

For the approach being used here, the degrees of freedom associated with eachestimated Si is assumed large enough to justify using t=2 in the analyses thatfollow.

Table 2 provides a list of the partial derivative of equation (1) with respect to eachterm of interest and provides initial estimates of the bias and precision errors foreach of these terms.

5

Term

1 a

2 v

3 m

4 P,

5 P~

6 T1

7 Tz

‘WSRC-RP-99-O0595 ‘ ‘Revision O

Table 2: Information Associated with the Propagation of Errors95%Bound for 95% Bound for 1 Standard 1 Standard

Partial Derivative Bias, Bi Bias, Bi Deviation Deviation

Units (relative) (absolute) Precision, Si Precision, Si(relative) (absolute)

–P, .v

RT,270 0.004 2% 0.004

m.P2 a.P,cc

RT23?70

‘RT11 3% 1

P2. V

RT25% 0.01 5% 0.01

–a. Vtorr

RT11% 7 1% 7

tomm.V

RT21% “ 7 1% 7

‘KaP,. V

0.33% 1RT:

0.33% 1

‘K–m. P2. V

0.33% 1 0.33% 1RT;

The estimates of the uncertainties presented in Table 2 will be the basis forderiving the uncertainties, via error propagation, for the r’s resulting from these9975 package tests.3 As indicated in this table, relative and absolute errors will beconsidered in this analysis for each measurement.

There is a need to understand the difference between using relative and absoluteerrors to represent or model these uncertainties. Let the true value for ameasurement be represented by MT. If the size of the errors afflicting MT isaffected by the size of MT itself, then the use of relative errors would beappropriate. If the size of the errors is unaffected by the size of MT, then the useof absolute errors is appropriate.

For example, the value of the sample volume, V, varies from a low of 14.43 cc toa high of 123 .67cc over these tests. The bias, when considered as a relative 3%error, would range from 14.43 x 0.03 = 0.433 cc to 123.67 x 0.03 = 3.71 cc. Thebias, when considered as an absolute error, would be a constant 1 cc. Thestandard deviation of the random errors afflicting V, when considered as a relativeerror, would range from 14.43 x 0.03 = 0.433 cc to 123.67 x 0.03 = 3.71 cc. Thestandard deviation would be a constant (an absolute) 1 cc when these randomerrors are assumed to be unaffected by the size of V.

It is not unusual for the absolute errors to dominate when MT is at the low end ofthe range of its possible values while relative errors dominate when MT is at thehigh end of its range. In the discussion that follows, error propagations areconducted that consider various combinations of these errors as relative orabsolute, since the true models for these uncertainties are not known.

3These estimates of bias and precision were developed during discussions of these issues

and are felt to be representative of these measurement uncertainties.

6


Correlations among the biases and any among the random errors afflicting themeasurements for any one test would be limited to the beginning and endingtemperatures and the beginning and ending pressures. It is expected that suchcorrelations would be positive in sign. Note, however, that the partial derivativesfor the two pressures and those for the two temperatures are of different signs.This implies that any such correlations among these biases and/or among these -random errors would tend to reduce the uncertainty of the resultant, r.

SIGNIFICANT DIFFERENCES IN MOLES OF OXYGEN

In the analyses that follow, the focus is on two primary situations. The firstassumes that there are no correlations among these measurements and that theuncertainties of Table 2 are representative. In this situation, the error propagationis to be developed (i.e., the choice between each relative and absolute error modelis made) to provide an upper bound on the uncertainties for the r values (at a 95%confidence level). The second situation reflects highly correlated errors betweenthe two temperature measurements, highly correlated errors between the twopressure measurements, and uncertainties for all measurements smaller than thoseappearing in Table 2. The intent is to use the second situation to conduct asensitivity analysis on the assumptions used in the first situation.

Table 3 provides the results for the first situation, the upper bounding case. Itidentifies each of the 9975 package tests, provides values for the 7 measurementterms from equation (1), evaluates the corresponding value for r, and propagatesthe uncertainties of the measurements into the resulting r, selecting the maximumof the relative and absolute error models for each measurement. No correlationsamong the biases or random errors are considered in this table.

The next to the last column of this table provides the uncertainty of the measureddifference, r, in 02, at a 95% confidence level. This is a +/- uncertainty for thederived value of r. The last column indicates the results of assessing thedifference between the calculated value of r and zero in light of r’s uncertainty.Three labels are used for the rows of this last column. If the value of r issufficiently greater than zero, the label “02 generated” is used for the row. If thevalue of r is sufficiently less than zero, the label used is “02 depleted.”Otherwise, the label “No difference” is used for the row.

Exhibit A6 in the Appendix provides a plot of the results of Table 3 by test. Itshows the upper and lower error bounds for each test plotted around zero. If thecalculated value of r falls within this interval, there is no significance differencebetween the initial and final moles of 02. A plotted value about the upper limit,indicates that the final moles of 02 is significantly greater than the initial for thattest, and a plotted value below the lower limit indicates that the final 02 moles aresignificantly less than the initial moles. Thus, this plot provides a graphicalrepresentation of the significance of the 02 difference relative to the 95’%0uncertain y limits.

7

WSRC-RP-99-O0595 ‘Revision O

Table 3: Results of Bounding Error Propagation by Test Number957. r value

UncertaintyTest PI

relative to

v T1 P2 T21 0.2:946

R for r

752.2

zero at9570

34.11 296.6 0.;88 743.2 295.7 62324,73 -0.&Q32 0.00003470 No difference

2 0.20946 741.9 63.86 294.7 0.179 711.8 297.2 62324.73 -0.000101 0.0CO06254 0, Oepleted

3 0.20946 740.9 30.50 299.3 0.211 741.3 295.9 62324.73 0.000CF35 0.IXX303222 No difference

4 0.20946 748.3 30.90 298.5 0.201 751.5 295.4 62324,73 -01300007

5 0.209460.00003182 No rfifferenc.e

755.5 29.81 297.3 0.228 891.3 295.5 62324,73 0.000074 0.CCW4012 Oz Generated6 0.20946 775.7 62.33 295.5 0.039 774.7 294.5 62324.73 -0.W7 0.0CO137169

7 0.20946 649.4 49.71 296.2

Oz Oep[eted0.036 808.1 331.0 62324.73 -0.0002%

8 0.20946

o.o@051 45 Oz Depleted

750.2 64.10 295.6 0.196 735.1 295.7 62324.73 -OSQCK346 0.0W36467

9 0.20946 734.5 62.91 299.1

No difference0.202 733,3 298.2 62324.73 -OCOIX118

10 0.20946

0.0CO06303 No difference

746.5 43.46 298.5 0.202 746.5 295.8 62324.73 -OI3OOO1O

110.00004463

0.20946 755.7 38.51 296.4No difference

o.197 749.7 295.9 62324.73 -o.tN3022 0.CHM03948

12 0.20946 756.6 30.72 297.5

No difference

0.2 753.7 296.1 62324.73 -0. CCO012

13 0.20946

0.00003161762.3

No difference

51.66 302.1 0,031 655.9 295.9 62324.7314 0.20946

-0.0C0381 0.CPW35323765.1

02 Depleted

64.37 296.3 0.167 975.2 329.5 62324.73 -0.CCO048 0.00007500

15 0.20946 754.1

No difference

65.63 299.6 0.117 806.3 327.6 62324.73 -0.CKM252 0.0VWK%9516 0.20946

02 Depleted

760.2 30.78 296.1 0.155 753,2 314.3 62324.73 -OMIO082 0.COC03058 01 Depleted

17 0.20946 762.2 42.04 298.0 0.206 779.1 297.2 62324.73 0.0COO03 o.m546 No difference

18 0.20946 760.0 30.34 298.0 0.155 1179.8 296.4 62324.73 0.oOoo40 0.COO0459319 0.20946 751.7 52.40 298.4

No difference0.182 744.5 297.4 62324.73 -0. CCO061 0.CCG135307 Oz DcpIeted

20 0.20946 753.4 53.82 297.6 0 1178.3 321.3 62324.73 -0.0W3458 0.00008059 O* DepIeted

21 0.20946 744.0 25.98 298.4 0.06 803.2 323.0 62324.73 -0,000155

22 0.209460.0CO02898 O* Depleted

749.4 43.03 298.3 0.154 742.1 298.023 0.20946

62324.73 -0.000099758.2

0.00W4357 O* Oepleted31.95 299.0 0.119 806.3 307.8

2462324.73 -0.OCO112 o.o13003417

0.20946 764.4

Oz Oepleted43.83 298.1 0.197 764.3 297.8 62324.73 -0.0W022 0.WO04545 No difference

25 0.20946 749.5 14.43 295.9 0,126 800.2 324.7 62324.7326 0.20946

-0.0CO051 0.IXW1633752.6 25.67

O* Depleted296.2 0.162 789.2 317.1 62324.73 -0.C03053

‘2a 0.20946 758.2 68.910.00002617 Oz Ocpleted

296.7 0.242 829.8 297.9 62324.73 o.m153

29 0.209460.00009085

768.4 27.47

Q Generated

371.7 0.133 341.5 419.5 62324.73 -0.00014330 0.20946 755.8 63.26

0.00001726 Oz Depleted297.8 0.165 724.6 297.6

31 0.2094662324.73 -0.000132 0.000M300

733.8 26.22

O* Oepfeted

369.5 0.205 738.8 367.5 62324.73 -o.m2 0.00002169 No difference

32 0.20946 753.9 91.65 297.5 0.129 772.2 296.933 0.20946

62324.73 -0.000287760.0

0.00009684 02 OepIetcd38.54 298.8 0.202 751.8 2%.8

3462324.73 -0.000013

0.209460.00003982 No difference

768.9 38.98 298.9 0.202 760.5 296.9 62324.73 -0.00C01335 0.20946

0.0W04072745.8

No difference

53.04 296.4 0.189 755.3 297.436

62324.73 -o.oom340

0.209460.00005432

748.5

No difference

61.32 297.9 0.013 3843.2 324.537 0.20946

62324.73 -0.000366 0.131Y326301741.6 26.49

02 Depleted

297.4 0.2 813.1 316.138 0.20946

62324.73 -o.oocH303 0.CKX302739744.9

No difference

44.90 297.4 0.141 802.2 297.9 62324.73 -0.000104

39 0.20946 752.40.00W4835 Oj Oepleted

46.04 297.4 0.208 758.3 297.8 62324.73 O.owooo

40 0.20946 759.70.0W34889 No difference

46.27 297.9 0.201 805.8 298.0 62324.73 0.00000741 0.20946 750.0 19.25

0.0CW15tY28 No difference

298,2 0.199 742.32 2%.4 62324.73 -0.00CO09

42 0.20946

0.00C01952

751.6 72.90 301.3

No difference

o.197 739.1 296.9 62324.7343 0.20946

-0.COO038 0.CCQ07337742.4 70.24 303.0

No difference0,209 730.8 2%.9 62324.73 0.00ooo1

44 0.20946

0.00007241

750.5 123.67 300.6

No difference

0.186 722.7 297.4 62324.73 -0.0CO141 0.00012212 Oz Depleted

45 0.20946 756.9 37.51 298.5 0.21 782.5 297.4 62324.73 O.oowl 3

46 0.209460.000134130 No difference

763.9 38.12 298.9 0.211 788.3 296.9 62324.73 0.000015

47 0.209460.00004253

749.7 18.% 297,9

No difference0.073 1197.3 370.0 62324.73 -0.00C088

48 0.209460.00002573 o* Dep!-eted

752.4 71.59 297.7 0.227 1095.2 336.749

62324.730.20946

o.oof3240744.4

0.00010292 o* Generated

69.% 297.8 0.297 1092.7 333.9 62324.73 0.W3503

50 0.20946 748.8 122.76 298.20.CH3013241 o* Generated

0.189 736 298.451

62324.730.20946

-0.000118755.7

0.rY3012278 No difference18.74 298.1 0.199 753.4 298.1 62324.73

52-0.000008

0.209460.00001917 No difference

762.5 45.15 298.8 0.2014 747.9 298.453

62324.73 -0.CM022 0.000046160.20946 754.9 18.74

No difference297.6 0.13 872.6 338.2 62324.73 -0.000059 0.CKH302052

54 0.20946 754.7

o* Oepfeted

31.56 298.1 0.2 775.2 315.6 62324.73 -o.oOco2055 0.20946 743.3

0.ooO03153 No difference

71.49 298,4 0.19 744.9 298.156

62324.730.20946

-0.W3054 0. COO07213759.8 37.50 298.4

No difference0.2 774.6 297.5

57 0.2094662324.73 -0.0CW08 0.CW03931

774.9

No difference

18.49 298.3 0.101 1048.9 3C0.6 62324.73 -0.000057

58 0.209460.IMO02561

750.0 31.27 298.8 0.CO126

Oz Depleted

750.3 299.3 62324.73 -o.oOOo059459 0.20946

0.00003234742.4 59.55 298.2

No difference0.162 1019 322.6 62324.73 -o.oOc4309 0.00007296 No difference

Table 4 repeats the conclusions from Table 3 and adds the results from three moreapproaches to the error propagation for equation (1). The columns of Table 4headed “Correlations With Uncertainties” reflects the results of an errorpropagation using the information of Table 2 and assuming perfect positivecorrelations between the biases for the two pressure measurements, between thebiases for the two temperature measurements, between the random errors for thetwo pressure measurements, and between the random errors for the twotemperature measurements. The next pair of columns shows the results from the

8


approach of assuming these same correlations but reducing the uncertainties ofTable 2 by a factor of 2. The last pair shows the results from the errorpropagation assuming these same correlations and reducing the uncertainties ofTable 2 by a factor of 5. For these correlated situations, the minimum of therelative and absolute error models is selected to represent each and everyuncertainty term of equations (3) and (4) involved in the error propagation.

Table 4: Comparisons Among The Error Propagation ApproachesCorrelated With Uncertainties Correlated With Uncertainties

Boundinp Situation Perfectly Correlated Situation Reduced by a Factor of 2 Reduced by a Factor of 5

95% r value 95% r value 95% r value 95% r valueUncertain y relative to Uncertainty relative to Uncertainty relative to Uncertain y

Test

refative tofor r zero at 95% for r zero at 95%

-O&032for r zero at 95% for r zero at 95%

1 0.0CO03470 No difference o.ooO03139 02 Depleted 0.01M31569 02 Depleted 0sXW30628 02 Depleted

2 -0.mlol 0.00C06254 02 Depleted 0.00005424 02 Depleted 0.00002712 02 Depleted 0.00001085 02 Depleted

3 0.000005 0.COO03222 NO difference 0.0@W2935 No difference 0.KuXt1468 No difference 01MXKM3587 NO difference

4 -OSX30007 0.00003182 No difference o.ooO03017 No difference o.o@301509 No difference o.txtooo@3 02 Ocpleted5 0.000074 o.oo@34012 02 Gerrcrated 0J30003407 02 Generated o.ocoo1704 02 Gerrcrated o.0000&581 02 Generated6 -0.W7 0.WM37 169 02 Depleted 0.00003197 02 Depleted 0.0COO1598 02 Depleted o.m39 02 DepIeted

7 -0.0C0296 0.00C05145 02 Depleted o.m306 02 Depleted O.ml 153 02 Depleted 0.0QOO0461 02 Depleted8 -0.0CO046 o.cooo6467 No difference 0.00CM046 No difference 0.00003023 02 Depleted o.@3txl1209

9

02 Dcpleted

-0.00CO18 0.00006303 No difference o.ootx35957 No difference 0.00002978 No differerrcc 0J30001191 02 Depleted10 -O.OOOO1O 0.00004463 No difference 0.001M4214 NO difference 0.0CM2107 No difference 000000843 02 Depleted

11 -0.00C022 0.00003948 No difference 0.00003708 No difference 0.01XX31854 02 Depleted 0sX3CO0742 02 Depleted

12 -o.otxx312 0.0Wt03161 No difference 0.00003006 No difference O.OCQOI503 No difference 0C43WX601 02 Depleted13 -0.000381 0.00005323 02 Depleted 0.WO02698 02 Depleted 0.0CGO1349 02 Depleted o.cKtoco540 02 Depleted

14 -o.m8 0MH307500 No difference 0.00006116 No difference 0.00003058 02 Drpleted 0.CH300122315 -0.0C0252 0MH306695

02 Depleted02 Depleted 0.00004227 02 Depleted o.fM302114 02 Depleted 0.001M3845 02 Dep[eted

16 -0.0Mt082 0.03003058 02 Depleted 0.00002399 02 DepIeted O.otmol 200 02 Depleted 03QOO0480

17 0J300003 0JX3004546

02 DepletedNo difference 0.00004217 No difference o.C@302108 No difference

180.000C0843 No difference

o.o@3040 0.00004593 No difference 0.0CO03499 02 Generated o.otKt1750 02 Generated o.ctoooi3700 02 Generated

19 -0.000061 0.00005307 02 Depleted 0.00004669 02 Depleted 0.IXK302334 02 Depleted

20 -0.000458 0.000080590.oOoo0934 02 Depleted

02 Depleted o.ooi302909 02 DepIeted 0.0M)01454 02 Depleted 0.000C0582

21 -0.000155 0.COO0289802 Depleted

02 Depleted 0.01XD1593 02 Depleted 0.0WO0797 02 Depleted22 -o.lxtcto99

0.00000319 02 Dcp!eted0.00004357 02 Depleted 0.00(M33370 02 DepIeted 0.WX301685 02 Depleted 0J300C0674

23 -0.OCO112 0.00003417

02 DepIeted

02 Depleted 0.00002258 02 DepIeted O.COOO1129 02 Depleted 0.00000452 02 Depleted

24 .o.cooo22 o.t3&304545 No difference 0.00004266 No difference o.m2133 02 Depleted o.m853 02 Depleted

25 -0.00C051 0.01Y301633 02 Depleted O.COOO1O18 02 Depleted o.m509 02 Depleted o.otxm204 02 Depleted

26 -0.00C053 o.m617 02 Depleted 0.00002098 02 Depleted o.oolxtlo49 02 Depleted28 0.W153 0.WO09085

0.00003420 02 Depleted02 Generated 0.00C07288 02 Generated

29 -0.000143o.ocK303644 02 Generated

0.00001726 02 Depleted0.00001458 02 Generated

0.00001366 02 Depleted 0.0CCO13683 02 Depleted o.m273

30 -0.WIOl32 0J3000630002 Depleted

02 Depleted o.m5112 02 Depleted 0.00002556 02 Depleted31 -0.000002

0.OOOO1O22 02 Depleted0.00002169 No difference 0.00002024 No difference o.o&301012 No difference o.ooOO0405 No difference

32 -0.000287 0.MO09684 02 Oepleted 0.00006468 02 Depleted33

0.00003234 02 Depleted 0.00001294

-0.000013 0.WM3398202 Depleted

No difference o.lxKto3755 No difference 0.0!XX31878 No difference34 -o.oOcn313 0.00C04072

o.m75] 02 DepletedNo difference 0.00003838 No difference 0.(MM31919 No difference 0.m768 02 Depleted

35 -0.000040 0.00005432 No difference o.ooco4931 No difference 0.IXXK12466 02 Depleted o.000txW86

36 -0.000366 0.0!X326301 02 Depleted

02 Depleted

0.00003163 02 Depleted O.OQCOl582 02 Depleted

37

o.000rM33 02 Depleted

-0.0WO03 0.0W3’2739 No diffe~nce 0.COO02605 No difference 0.0WH31302 No difference

38 -o.otxtlo4 o.ootM48350.000 C0521 No difference

02 Depleted 0.C4XM3480 02 Depleted O.OCOOI740 02 Depleted

39

0.00000696

o.otxn300 0.WX0488902 Depleted

No difference 0.00004501 No difference 0.00002251 No difference o.oOo@900 No difference

40 0.000007 0.0CO05028 No difference o.txtoo4764 No difference 0.CCC02382 No difference o.tMoG(t953 No difference41 -o.oOtxo9 0.00i301952 No differcrrce o.CCn301849 No difference 0.00M0924 No difference o.m370

42 -0.000038 0.00007337

02 Depleted

No difference 0.0LW06895 No difference 0.00003447 02 Depleted 0J30001379 02 Depleted

43 o.cKtoool 0.CCC07241 No differcrrce 0.C0306652 No difference 0.WO03326 No difference44 -0.0W141 0.00012212 02 Depleted

0.00001330 No difference0.00010926 02 Depleted 0.00005463 02 Depleted 0.WO02185

45 0,0COO13 O.ml 30

02 Depleted

No difference o.otMo3771 No difference O.(HMO]885 No diffe~nce46 0.000015 0.00004253

o.m754 02 GeneratedNo difference 0.CGC03865 NO difference 0MO01933 No difference o.m773

47 -0.000088

02 Generated

0.COIXt2573 02 Depleted o.ooOO1215 02 Depleted o.#ooo607 02 Depleted 0.00000243 02 Dep lewd

48 0.000240 O.CCO1O292 02 Generated 0.00008658 02 Generated 0.0W04329 02 Generated 0.01XtO173249 0.000503 0.tXW13241 02 Generated

02 Generated

0.0CO08592 02 Generated 0.CY3004296 02 Generated 0.0000171850 -0.000118 O.COO]2278 No difference 0.00011134

02 Generated

02 Depleted 0.00005567 02 Dcple$ed

51

o.m227

-o.m8 o.otMo1917 No difference

02 Depleted

O.tXWOl815 No difference52

0.0QW09Q7 NO difference o.m363-o.otMo’22 0.0Gi304616 No difference 0.00004361

02 DepletedNodifference 0.06002181 No difference

53 -0.001)059 0.00002052 02 Depleted

0.0WO0872

0.00001369

02 Depleted

02 Depleted 0.0QOO0685 02 Depleted54 -0.000020 o.m31 53

0.-74No difference 0.CCO02994

02 Depleted

No difference o.m1497 02 Depleted55 -0.000054 0.MXX37213

o.m599No differexe 0.00W6578

02 Depleted

No difference 0.00003289 02 Depleted

56 -o.m8 0MO039310.00001316

No difference

02 Depleted

0.00003739 No difference 0.00@31870 No difference57 -0.00C057 0.00i302561

o.m74802 Depleted 0.00001397

02 Depleted02 Depleted 0.000Q0698 02 Depleted o.m279 02 Dep leted

58 -o.m594 0.00@3138 No difference 0.00003015 No difference 0.00001508 No difference o.000xt60359 -0.00WKW

No difference

0.00007296 No difference o.otMo5799 No difference o.m2900 No difference 0.00001160 No difference

9

WSRC-RP-99-O0595 - “Revision O

Table 5 summarizes the results from the various approaches to propagating theerrors of Table 2 into equation (1). This table identifies those tests (by number)that reveal an 02 change significantly nonzero (at the 95% confidence level). Theaverage of the uncertainties across all of the tests is also provided for eachsituation.

Table 5:Description of Propagation

Approach

Bounding CaseUsing Maximum of Relative versus

Absolute ErrorsCorrelated Errors Using Minimumof Relative versus Absolute Errors

Correlated Errors Using Minimumof Relative versus Absolute Errorswith Initial Uncertainties Reduced

by a Factor of 2Correlated Errors Using Minimumof Relative versus Absolute Errorswith Initial Uncertainties Reduced

by a Factor of 5

lmmary InformationTests showing

an increased 02 level

5,28,48,49

5, 18,28,48,49

5, 18,28,48,49

5, 18,28,45,46,48,49

-om Error PropagaticTests showing

a decreased Oz level

2,6,7, 13, 15, 16,19-23,25,26,29,30,32,

36,38,44,47,53,571,2,6,7, 13, 15, 16, 19-

23,25,26,29,30,32,36,38,44,47,50,53,57

1,2,6-8, 11, 13-16, 19-26,29,30,32,35,36,38,42,

44,47,50,53-55,57

1,2,4,6-16, 19-26,29,30,32-36,38,41,42,44,

47,50-57

s

Average Uncertainty in 02Change (moles)

0.00005541

0.00004151

0.00002075

0.00000830

In comparing the test conditions indicated in Table A2 to the anticipatedoperational window for the 9975 package, several of the tests are deemedunrepresentative of the operational conditions or are considered to have led toquestionable outcomes. The tests deemed unrepresentative include 29,35,40,46,and 52 (due to under injection of the sample in the gas chromatographymeasurement), 5 and 18 (due to excessive moisture), and 28, 35, 42, 43, 48, and49 (due to the samples not having sand, slag, and crucible, SS&C, components).

Exhibit A7 in the Appendix provides a plot the 02 changes for those remainingtests that are considered to be representative of the 9975-package operationalconditions. Also, shown on this plot are the corresponding upper uncertaintylimits for these oxygen differences. This plot shows that none of these tests have02 changes indicating significant (at the 9590 confidence level) increases inoxygen.

The average 02 change for these tests is -0.00009 moles, and the averageuncertainties corresponding to the error propagation approaches of Table 5 rangefrom a high of 0.000053 moles to a low of 0.0000094 moles. Expressed asrelative uncertainties, these high and low values are 59$Z0and 10!ZO,respectively.

Exhibit A8 in the Appendix provides a plot of the initial versus final moles ofoxygen for these tests. A paired t-test for these data (assuming that these testresults are representative of --- i.e., a random sample from --- the intendedoperational window for the 9975) is also provided in this exhibit. This statisticaltest reveals that the null hypothesis of a zero mean difference between the initial

10

.WSRC-RP-99-O0595

Revision O

and final moles of oxygen (final – initial) for these experiments is stronglyrejected (the probability of obtaining these results by chance alone is 1 in 100,000if there is no difference in the quantity of 02) in favor of the hypothesis that themean oxygen difference is less than zero; i.e., in favor of the hypothesis that onaverage oxygen is depleted for these tests.

CONCLUSIONSA review of the oxygen data from the gas generation tests supporting the 9975SARP has been conducted including the development of an error propagation ofthe measurement uncertainties into the equation for the change in moles of 02.This analysis revealed tests with significant (at a 95% confidence level)differences between their beginning and ending moles of 02 based upon themeasurement and analytical uncertainties assumed in this report.

REFERENCES[1] Livingston, Ronald R., Gas Generation Test Support for Revision of 9975 SARP:

Task Technical and Quality Assurance Plan,” WSRC-RP-99-O01 64, February 18,1999.

SAS Institute, JMP@ Statistics and Graphics Guide, Version 3 of JMP, SAS[2Institute Inc., Cary, NC, 1995.

[3] Coleman, Hugh W. and W. Glenn Steele, Jr., Experimentation and UncertaintyAnalysis for Engineers, John Wiley & Sons, Inc., New York, 1989.

WSRC-RP-99-O0595 “ ‘Revision O


12

.


APPENDIX:

TABLESANDEXHIBITS

13

WSRC-RP-99-O0595 “Revision O


14

Appendix: Tables and Exhibits WSRC-RP-99-O0595 ‘ ‘Revision O

able Al: Test Measurementsby Test Number4

Test12345678910111213141516171819202122232425262829303132333435363738394041424344

Volume(cc)

34.1163.8630.5030.9029.8162.3349.7164.1062.9143.4638.5130.7251.6664.3765.6330.7842.0430.3452,4053.8225.9843.0331.9543,8314,4325.6768.9127.4763.2626.2291.6538.5438.9853.0461.3226.4944.9046.0446.2719.2572.9070.24123.67

Initial

(torr)752.2741.9740,9748.3755.5775.7649.4750.2734.5746,5755.7756.6762.3765.1754,1760.2762.2760.0751.7753.4744.0749.4758,2764.4749.5752.6758.2768.4755.8733.8753.9760.0768.9745.8748,5741.6744.97.52.4759.7750.0751,6742.4750.5

InitialTemperature

(“K)296.6294,7299.3298.5297.3295,5296.2295.6299.1298.5296.4297.5302.1296.3299.6296.1298.0298.0298.4297,6298,4298,3299.0298.1295.9296.2296.7371.7297.8369.5297,5298.8298.9296.4297.9297.4297.4297.4297.9298.2301.3303.0300.6

initialTotalmoles

I,388E-032.579E-031.211E-031.243E-031.215E-032.625E-031,749E-032.61OE-O32.479E-031.744E-031.575E-031.254E-032.092E-032.667E-032.651E-031.268E-031,725E-031,242E-032.118E-032.186E-031.039E-031.734E-031.300E-031.803E-035.865E-041.047E-032.825E-039.112E-042.576E-038.355E-043.726E-031.573E-031.609E-032.141E-032.472E-031.060E-031,804E-031,869E-031.893E-037.769E-042.918E-032.761E-034.954E-03

EstimateInitial N2

moles1.084E-032.014E-039.459E-049.705E-049.491E-042.050E-031,365E-032.038E-031.936E-031.362E-031.230E-039.788E-041,633E-032.082E-032.070&039.901E-041.347E-039.694E-041,654E-031.707E-038,1 15E-041.354E-031.015E-031.408E-034.579E-048. 172E-042.206E-037.1 15E-042,01 IE-036.524E-042.9 10E-031,228E-031,256E-031.672E-031.930E-038.276E-041.409E-031.459E-031.478E-036.066E-042,278E-032, 156E-033.868E-03

EstimateInitial 02

moles2.907E-045.403E-042.537E-042.603E-042.546E-045.499E-043.663E-045.467E-045. 192E-043.653EL043.300E-042.626E-044.381E-045,586E-045.552E-042.656E.043.614E-042.600E-044.436E-044.579E-042. 177E-043.633E-042.723E-043.777E-041.228E-042. 192E-045.918E-041.909E-045.396E-041.750E-047.805E-043.294E-043.370E-044.485E-045. 178E-042,220E-043.780E-043.915E-043.966E-041.627E-046. 112E-045.784E-041.038E-03

Final

(torr)743,2711.8741.3751.5891.3774.7808.1735.1733.3746.5749.7753.7655.9975.2806.3753.2779.11179.8744.51178,3803,2742. I806.3764,3800.2789.2829.8341.5724.6738.8772.2751.8760.5755.3

3843,2813.1802.2758.3805.8

742.32739. I730.8722.7

FinalTemperature

(“c)22.724.222.922.422.521.5105.522,725.222,822.923.122.997.8111.7109.224.223.424.425.194.725

96,924.892.694,424.999.324.694.523.923.823.924.4106.3106.124,924,825,023.423.923.924.4

FindTemperature

(“K)295.7297.2295.9295.4295.5294.5331.0295.7298.2295.8295.9296. I295.9329.5327.6314.3297.2296.4297.4321.3323.0298.0307.8297,8324.7317.1297.9419.5297,6367.5296.9296.8296.9297.4324.5316.1297.9297.8298.0296.4296.9296.9297.4

FinalTotalmoles

1.376E-032.454E-031.226E-031.261E-031,443E.032.631 E-031.947E-032.557E-032.482E-031.760E-031.566E-031.255E-031.837E-033.057E-032.592E-031.184E.031.768E-031.938E-032. 105E-033. 167E-031.037E-031.7 19E-031.343E-031,805E-035.705E-041.025E-033.080E-033.588E-042.47 lE-038.457E-043.825E-031,566E-031.602E-032,161E.031.165E-021.093E-03I .9401+031.881E-032.007E-037.736E-042.912E-032.774E-034.822E-03

%Hz ‘%02 %N20.55 18.80 84,000.00 17,90 84,500.00 21,10 82,300.00 20.10 82.5010.80 22.80 61.704.20 3.90 81.603.70 3,60 87,000.05 19.60 86.000.08 20.20 85,100.62 20,20 83,800.26 19.70 88.100.54 20.00 84.806.19 3,10 90.800.89 16.70 80.CQ0.00 11.70 82.600.22 15,50 78.201,64 20,60 79.60

24,15 15.50 53.100.00 18.20 83,8080.fM 0.00 23,602.60 6.OQ 95,600.13 15.40 86.301.60 11.90 88.605.00 19.70 76.602.17 12.60 82.701.19 16,20 79,401.82 24.20 68,200.46 13.30 85.801.27 16.50 75.800.03 20.50 76.(X38.13 12.90 78.501.60 20.20 76.400.20 20.20 76.900.00 18.90 55.20

74.70 I .30 17.900.40 20.00 64.207.40 14.10 77.706.50 20.80 72.103.00 20.10 54.400.70 19.90 81.200.10 19.70 80,000.00 20.90 79.500.20 18.60 82.40

FinalHZ

moles7.566E-060,000E+OOO.COOE+OO0.000E+OO1.558E-041, 105E-O47.206E-051.278E-061,986E-061.091 E-054.07013066.775E-061,137E-042.721E-050.000E+OO2.604E-062.900E-054.680E-040.000E+OO2.534E-032.695E-052.235)3-062. 149E-059.024E-051.238E-051.220E-055.605E-051.650E-063.139E-052.537E-073.109!5-042.506E-053,204E-060,000E+OO8,703E-034.373E-061.436E-041.223E-046.022E-055.415E-062.912E-060.000E+OO9.644E-06

Finalo~

moles2,586E-044.393E-042.587E-042.535E-043.289E-041.026E-047.011 E-055.OIIE-045.014E-043.555E-043.084E-042.509E-045.696E-055, 105E-O43.032E-041,835E.043,643E-043,003E-043.831 E-040.000E+OQ6.220E-052.648E-041,598E-043,556E.047. 189E-051,661 E-047.453E-044.772E-054.078E-041.734E-044.934E-043. 164E-043.236E-044.085E-04I,515E.042, 187E-042,735E-043.913E-044.035E-041.539&045.736E-045.798E-048.969E-04

FinalN*

moles1. 155E-032.074E-031,009E-031,041 E-038.901 E-042. 147E-031.694E-032. 199E-032, 112E-031,475E-031.379E-031.064E-031.668E-032.446E-032.141 E-039.256E-041.408E-031.029E-031.764E-037.474E.049.91 OE-O41.484E-031. 190E-031.383E-034.71 8E-048. 140E-042. IOOE-033.078E-041.873E-036.428E-043.002E-031.197E031.232E-031.193E-032,086E.037.019E-041.507E-031.356E-031.092E-036.282E-042,330E-032.205E-033.973E-03

A O,moles

(final-initial)-3.2 12E-05-1 .OIOE-044.942E-06-6.814E-067.434E-05-4.473E-C4-2.962E-04-4.560E-05-1 .780E-05-9.794E-06-2. 157E-05-1 .164E-05-3.81 lE-04-4.809E-05-2.520E-04-8.211 E-052.889E-064.029E-05-6.057E-05-4.579E-04-1.555EJ34-9.853E-05-1.125E-04-2.216E-05-5.095 E-05-5.31 2E-051.535E-04

-1 .431E-04-1.318E-04-1 .621E-06-2,872E-04- 1.3~E-05-1 ,339E-05-4.003E-05-3.663E-04-3.334E-06- 1.044E-04-2.066E-076.940E-06-8,780E-06-3.754E-051,384E-06

- 1.408E-0445 37.51 756.9 298.5 1.526E-03 1.192&03 3. 196E-04 782,5 24,4 297.4 1.583E-03 2.30 21.00 76.80 3.642E-05 3.325E-04 1.216E-03 1.289E-05

—4 Test 27 was unsuccessful due to equipment failure.

15

Appendix: Tables and Exhibits WSRC-RP-99-O0595Revision O

‘able Al: Test Measurements by Test Number (continued)

Initial Initial Initial Estimate Estimate Final Final Final Final Final A O,Volume Pressure

Final FinalTemperature Total Initial N2 Initial 02 Pressure Tempemt ure Temperature

Test (cc) (torr)Total

(“K)Hz 02

molesN* moles

moles moles46 38.12

(torr)763.9

(“c) ~K) moles 90H2 %02 90Nz298.9

moles moles1.563E-03 1.221 E-03 3.274E-04 788.3

moles23.9

47296.9 1.624E-03

(final-initial

18.96 749.7 297.91.20 21.10 62.10 1.949E-05 3.427E-04 1.t309E-03

7.654E-04 5.977E-04 1.603E-04 I 197,31.524E-05

97 370,0 9,842E-04 3.4048 71.59 752.4

7.30 81.80 3.346E-05 7, 185E-05 8,051 E-04 -8.847E-05297.7 2.903E-03 2.267E-03 6.081 E-04 1095.2

49 69.9063.7

744.4336.7

297.83,736E-03 0.00 22.70 74.00 0.MKtE+Oi3 8.480E-04 2,765E-03

2.804E-03 2. 189E-03 5.872E-042.399E-04

1092.7 60.950 122,76 748.8

333.9298.2

3.670E-03 1,50 29.70 66,40 5.506E-05 1,090E-03 2,437E-03 5,029E-044.946E-03 3.862E-03 1.036E-03 736

5125.4

18.74 755,7298.4

298, I4.858E-03 0,40 18.90 79.20 1.943E-05 9. 182E-04 3.848E-03

7.623E-04 5.952E.04 1,597E-04-1. 178E-04

753.452

25. I45.15 762.5

298. I 7.599E-04 1,50 19.90 73.40 1, 140E-05 1.512E-04 5,578E.04298,8

-8.435E-061,848E-03 1.443E-03 3,872E-04 747.9

5325.4

18,74 754.9298.4

297.61.815E-03 0,55 20.14 78.36 9.985E-06 3.656E-04 1,423E-03

7.627E-04 5.956E-04 1,598E-04-2. 154E-05

872.654

65.231.56 754,7

338.2 7.758E-04 1.32 13,0Q 85.OQ 1,024E-05 1.009E-04 6,594E-04 -5,891E-05298.1 1.282E-03 1.00IE-03 2,686E-04 775.2

5542.6

71.49 743.3315.6

298.41.244E-03 0,00 20.0i3 74.00 0.0t30E+tX3 2.488E-04 9,205E-04 -1 ,977E-05

2.857E-03 2.231E-03 5.985E-04 744.956

25.137.50

298.1 2.866E-03 0,36 19,00 84.01) 1.032E-05 5.446E-04 2.408E-03 -5,389E-05759.8 298.4 1.532E-03 1.196E-03 3.209E-04 774.6

5724:5

18,49 774.9297.5

298.31,567E-03 0,25 20.CO 84.Oi) 3,917E.06 3. 133E-04 1,316E.03

7.707E-04 6.018E-04 1,614E-04 1048.9-7.580E-06

27.6 300.6 1.035E-03 1.80 10,10 81.50 1,863E-05 1.046E-04 8,437E-04 -5.687E-0558 31.27 750.0 298.8 1.259E-03 9,83E-0459

2.64E-04 750,3 26.359.55 742.4

299.3298.2

1,258E-03 0,00 20.50 78.10 0.000E+i13 2,58E-042.379E-03 1.857E-03 4.983E-04

9.82E-04 -5.945E-061019 49.6 322.6 3.018E-03 0.70 16.20 81.60 2.113E-05 4.890E-04 2.463E-03 -9.281E-06

16


Table AZ: Description of 9975 Test by Test NumbersRun Description Time Container Grams Bulk Measured Temp Run

#Sample# Hz 02 Nt C02

2/20/99Start --Set 1 (days) Volume PU02N*O

Weight(g)co sum

Volume f’c) # 2/20/99 Start -. Set 1 (Vol70 ) (Vol%)

I Pu02+ RF MgO sand & crucible(VOI?ZO) (VOI%) (Vol’70)

8.83 25CC(Vol%)

9.59(Vol%)

37.83 34,11 ambient 1 3-1236372 Pu02+ calcined CaO + Ca(OH)2 8.92

0.55 I 8.8 84 050CC

o8.85

035.80 63.86

103.35ambient

32 3-123636

Pu02 Stored over dessicant 9.650.00 17.9 84,5 0

5CCo

7.650

7.65 30,50102.40

ambient 3 3-1236354 Pu02 stored in 76%RH humidor 9.71

0.005CC

21.1 82.3 0.05 0 08.54 8.54 30.90

103.45

5ambient 4

Pu02 - 10% H20 added3-123634

6.660.00

5CC20.1 82.5 0.16 0

7.570

7.57 29.81102.76

ambient 56 Standard Gas 3.73 50CC

3-1236330.00

10.80 22.8 61.7 0. I o 00.00 62.33

95.40ambient 6 3-123638 4,20 3.9 81.6 1.8 0.5 1.2

31U99 Start -- Set 293,20

3/1/99 Start.. Set 27 Standard Gas + Heat 6.31 50CC

0.000.00 0.00 49.71 90

87 3-123639

#2 stored at 100%RH 6.143.70 3.6 87

50LX 7.73NR

31.30NR

64.104,06 98,36

ambient 8 3-1236409 Po02 + 30g CaF2 6.83

0.05 19.6 86 0.150CC

o 09,83 39.85 62.91

105.75ambient 9 3-123641

10 Pu02+Ca(OH)2 & MgO Crucible 5.75 25CC0.08 20.2 85. I 0,09 0.02 0

7.90 15.80 43,46105.49

ambient 10 3-12364211 #l storedat lW%RH 6,12 25CC

0.62 20.2 83.8 0.06 0 09.32 36.76 38.51

104.68ambient 11 3-123643

12 Pu02 storedat 100%RH 6.82 5CC0.26

9.5219.7

9.5288.1 0.05

30.720.04 4.28 112.43

ambient 12 3-123644 0.543/8/99Start --Set3

20 84.8 0.12 0.12 0 105.583/8/99Start -. Set3

13 44gof RF SS&C sample H6 7.88 50CC 15450 43.84 51.66 ambient 13 3-123645 6.19 3.1 90,814 #9 heated 7.88 50CC

0.03 1.6 09.83 39.85 64.37 90

101.7214

15 #8 heated3-123646 0.89 16.7 80

8.16 50CC5.2 0.25 0

7.73 31.30 65.63 90103.04

15 3-12364716 Pu02 stored at IOO%RH+ Heat

O.OQ 11,7 82.6 07.77

05CC

o7.26 7.26 30.78 90

94.3016 3-123648

17 Pu Cake (no added moisture) 7.610.22

25CC15.5 78.2 0.48

35.66”0.04 0

32.01 42.0494.44

amb]ent 17 3-12364918 #5 mixed with 2g Ca mstal 7.56 5CC

1.64 20.6 79.6 0.06 0.05 04.88 6.93 30.34

101.95ambient 18 3-123650 24.15

3/17/99 Start-- Set 415.5 53,1 0.03 0 0 92.78

3117r99 Start-- Set 4 0.0019 Cam at RTrepeat#14and#9 6.8 50CC 9.83 39.85 52.40 ambient 19 3-123651 0.oo 18.2 83.8 0.37 0.08 0 102.4520 #l 3 heated 6.8 50CC 15.50 43.84 53.82 90 2021 #10 heated

3-123652 80.00 0 23.6 06.81

0Iocc

o7.50 15.00 25.98

103.6JI90 21 3-123653

22 Pu02+Mg0 1:1 ratio2.60 6

6.81 25CC95.6 0.16 0.2 0

9.73 19.45 43.03104.56

ambient 22 3-123654 0.13 15.4 86.3 0.0923 #11 heated 6.78 IOcc

0.11 04.66 20.CQ 31.95

102.0390 23 3-123655 1.60 11.9 88.6 0.22

24 Pu02 + Mg(OH)2 6,79 25CC0.17 0

7.26 17.26 43.83102.49

ambient 24 3-123656 5.00 19.7 76.6 0.03 0.09 0 101.423~6199 Start-- Set 5 3/26/99 Start.- Set 5 0.oo

25 Pu02+ MEO with 10water 10.11 1Occ 6.60 25.00 14,43 90 25 3-123658 2.17 12.6 82.7 <.1 <.1 <.1 97.4726 Pu02+ M~O with med water 9,74 10CC 6.24 23.43 25.67 90 26 3-123659 1.19 16.2 96.79

4/6f99 Start-- Set 679.4 <. I <.1 <,1

4/6/99 Start.. Set 6

30 RFETSH2 7,69 50CC 8.18 43.10 63,26 ambient 30 3-12551431 Pu02+Mg0w/hiwater+heat

1.278.83

16.510CC

75.8 <.1 <.1 <,I#REF! 23.09 26.22

93.5790C 31 3-125515

32 RFETSH70.03 20.5 76

7.71<.1 <.1

100CC 6.77<.1

14.60 91.6596,53

ambiart 32 3-12551633 #l8 repeated 7.71

8.13 12.910CC

78.5 <.14.65

<.16.60

<,138,54

99.53ambient 33 3-125517

34 RFETSH81.6

7.6920.2 76.4 <.I

1Occ<.1

8,49<.1

10.80 38,9898.20

ambient 34 3-125518 0.2 20.2 76.9 <.1 <.1 <.1 97.304/16/99 Start -- Set 7 4/16/99 Start .- Set 7

36 RFETSSampleH2 5,61 50CC 8,18 43.10 61,32 90 36 3-125520 74.70 1,3 17,9 0.02 <.1 <.1 93.9237 #31 repeated 5.66 1Occ 6.15 23,09 26.49 90 37 3-125521 0.4038 Pu02 + 5%H20

205.69 25CC

64,2 0.03 0.02 <,19.66 10.29 44.90

84.65ambient 38 3-125522 7.40 14.1

4/23/99 Start -- Set 877.7 0.08 0.04 <.1 99.32

4/23/99 Start -. Set 8

41 Pu02+I 00%RH-2wceks 5,6 IOcc 10,08 10.08 19,25 ambient 41 3.125525 0.7 19.9 81,2 NR NR44 PuCake. 00 treatment like #17 5.77 IOocc 27.65 30.80

<0.1123,67

101.80ambient 44 3-125528 0.2 18.6 82.4 0.32 <0.1

45 PU02 + 2,5% water 5.77 IOCC 12,17<0.1

12.50101.52

37.51 ambient 45 3-125529 2,3 21 76,8 <0.1 <0.146 PU02+ 2.59” water 5.84 Iocc 9.83 10.32

<0.1 100.1038.12 ambient 46 3-125530 1.2 21. I 62.1 <0,1 <0.1 <0.1 84.40

5 Samples 28,29,35,40,42,43,48 and 49 contained materials that do not conform to the content description of SS&C residues.

17


Table A2: Descriptions of Tests by Test Number (continued)Run Description Time Cnntainer Granrs Bulk Measured

#Temp Run Sample # Hz O* Nz co~ N20 co

4/29/99Start -- Set9 (days) Volume Puozaum

Weight(g) Volume (“c) # 4129199 Start --Set9 (Vol%) (vow’.) (Vol%)47 Pu02+2.5%H20+Heat

(Vol%) (VOW.) (VOW.) (Vol%)6,77 10CC 12,17 12.50 18.96 90 47 3-125531 3.4 7.3 81.8 <0.1 <0.1 <0.1 92.50

50 PuCake-replicatel 6.76 1OQlx 27.34 30.46 122,7651 fkllrepeated

ambient 50 3-125534 0.46.76

18,9 79.2 <0.1 <0.1 <0,1 98.501Occ 10.08 10,08 37,11 ambient 51 3-125535 1.5

52 PuCake-replicate#2 6.7719.9

25CC73.4 <0.1 <0.1

14,98<0.1

16,6994.80

45.15 ambient 52 3-125536 0.55 20.14 78.38 <0.1 0.05 <0.1 99.105/18/99 Start -. Set 10 5/18/99 Start -- Set 10

53 #51 heated 7.95 1Occ 10.08 10.08 1&74 90 53 3-127169 1.32 13 85 <0.1 <0.1 <0.1 99.3254 Blank+Heat 7.95 10CC owl 0.00 31.56 90 5455 Pu02+13mg H20

3-127170 20 747.95 50CC

<0.112.57

<0.112.70

<0.1 94.0071.49 ambient 55

56 Pu02+15mgH203-127171

7.950:6 19 84

Iocc 10.42<0.1 <0.1

10.57<0.1

37.50103.36

5/26/99Start .- Set 11ambient 56 3-127172 0.25 20 84 <0,1 <0.1 <0.1 104,25

5/26/99Start --Set 1157 Pu02+15mgH20 7.75 1Occ 10.42 10.57 18.4958 Blank

90 578

3-127173 1.61Occ

10.10.00 0,00

81.5 <0.1 <0.1 <0.131.27

93.40ambient 58 3-127174 0

59 Pu02+13mgH20 7.78 50CC20.5 76.1

12.57<0.1 <0,1

12.70<0.1

59.55 9098.60

59 3-127175 0.7 16.2 81.6 2.8 0.31 <0.1 101.61

18


,

Exhibit Al: A Plot of the Initial versus Final 02 by Test Number

0.0014

0.0012

0.0010

0.0008

0.0006

0.0004

0.0002

0.0000

1 x49

-0.0002 I , , , , l“ 1’ 1’ 1’ , , , 1’ , r 1’ , , I I I I , , I , , , I

O 5 10 15 20 25 30 35 40 45 50 55 60

Test

19

Appendix: Tables and Exhibits

Exhibit A2: A Plot of the Change in 02 (Delta 02) by Test Number


.28

0.0006

0.0005- 949

0,0004-

0.0003-■48

0.0002-

g 0.0001 ,5

8 -0.0000 - “y’””w----wwF;-F----—:-”-”--T-”..w--M-T- ;---r--+””-+“--9:- --”-~,~ “,,,.,..,.,*.,~~ x E% ** ■ ■

4 -0.0001 - x +16 D. . .

‘ +23..

. . m. .

-0.0002-x15

-0.0003 . m■

-0.0004- .m .

-0s0005 , , , 1’ 1’ l“ , 1’ 1, , I , I 1’ I , 1, r 1’ , , 1’ I

O 5 10 15 20 25 30 35 40 45 50 55 60

Test

(Symbols used to identify tests as defined by the categories of Table 1)

20


*

Exhibit A3: A Plot of the Change in 02 (Delta 02) by Type Group —0,0006

0.0005- .49

0.0004-0.0003-

.480.0002- a28

g 0.0001- *5.

I -0.0002-0.0003;

n X15

-0.0004- J

■ .

-0.0005 1 I I I I

Other Pu Cake PU02 Pu02+CaF Pu02+Ca0 Pu02+Mg0

Type

i

Means and Std DeviationsExcludingHeatedTests

Level Number Mean Std Dev Number Mean Std DevOther 39 -0.00006 0.000176Pu Cake 4 -0.00007 0.000071PU02 4 -0.00003 0.000036 3 -0.00001 0.000002Pu02+Ca0 3 -0.00013 0.000107 2 -0.00007 0.000039Puo2+caF 3 -0.00004 0.000022Pu02+Mg0 5 -0.00005 0!000035 4 -0.00004 0.000015

21

Exhibit A4: A Plot of the Change in O? (Delta O?) bv HeadsDace Volume (cc


0.0014

0.0012

0.0010

0.0008

0.0006

0.0004

0.0002

0.0000

-0.00020

x49,,,,,/-

Appendix: Tables and Exhibits

I

I , I , I , I I , I20 40 60 80 100 120 140

v (cc)

Symbols are shaded to designate the categories of Table 1 (i.e., they are shaded as in Exhibit A3),

22,.


Exhibit A5: A Plot of the Change in 02 (Delta 02) by Total Sample Volume Percent

0.0006

0.0005 - ● 49

0.0004 -

0.0003 -■48

0.0002 -■28

g 0.0001 .5■

8 -0.0000 - ........—....=—...= ..__....-= ~.—,,.......— ...—...,-.-—..”m

, y-—-pmwm*-.mm-.-m.._...H_._ .. ...._● *

g *$&. =n?x4 -0.0001

● “+.16 ,. %23m .* .

-0.0002-X15

-0.0003 . ■

.-0.0004- ■

. m-0.0005 , , , I I , r I , , 1 , I , , , , I , , I , i , , ,

70 75 80 85 90 95 100 - 105 110

Sum of VOIYO

Symbols are shaded to designate the categories of Table 1 (i.e., they are shaded as in Exhibit A3).

23


Exhibit A6: A Plot of the Change in 02 (Delta 02) by Test Number with Bounding Uncertainties

0.00051

+

0.0004 1

-0.0002

1i)\)+ /

-0,0003 + +

-0,0004 + +

+ *-0.0005 , t [ , , , I * , , I I , I , r I , , I I , I , , , I , , , I

o 5 10 15 20 25 30 35 40 45 50 55 60

Test

EBold symbols are used to designate statistically significant (at the 95% confidence level) test results.

24

‘

,.

Appendix: Tables and Exhibits WSRC-RP-99-O0595 ‘ “Revision O

Exhibit A7: A Plot of the Change in 02 (Delta 02) by Test Numberwith Bounding Uncertainties for Representative Tests

0.0003

0.0002

0.0001

-0.0000

-0.0001

-0.0002

-0,0003

-0.0004

-0.0005

——...,.,.——“.”-A* +.-, .....-. --..-. -.”. .,-—.,..,.—-. ,, —._.- . . . . . ..-—.—

++*+

_“”r..~._ —.-”,,%- —_-.+-— .“. . ,- . ,_-+—. .,

+

--’’-77~

+ F

+ + + ++ ++++

++

+

+

+

++

+

+

++

+

+ +

-1 1 1 I 1 I i I I I

i 16 li 26 2i 30 35 40 45 50 55 60

Test

--

25

Appendix: Tables and Exhibits WSRC-RP-99-O0595 ‘ -Revision O

Exhibit AS: A Plot of the Initial Versus Final Moles of Oxygenfor Representative Tests

initial 02 (M) Bv final 02 (M)

0.0011

0.0009

0.0007

0.0005

0.0003

0.0001

-0.0001 fI 1 I I I I I I I 1 I I

-0.0001 .0002 .0005 .0008 .0011

final 02 (M)

Mean DifferenceStd Errort-RatioDF

I ~ Paired t-Test I

Paired t-Testfinal02 (M) - initial02 (M)

-0.00009 Prob > Itl0.000018 Prob > t

-5.0429 Prob < t45

0.00000800.99999600.0000040

Symbols are shaded to designate the categories of Table 1 (i.e., they are shaded as in Exhibit A3).

WSRC-RP-99-O0595 ‘ “Revision O

,

Distribution

N. M. Askew, 773-AA. L. BIancett, 773-AP. S. Blanton, 773-54AN. E. Bibler, 773-AM. A. Ebra, 773-42AT. B. Edwards, 773-42AF. R. Graham, 773-AS. J. Hensel, 773-42AS. M. King, 773-54AR. R. Livingston, 773-AJ. E. Marra, 704-TD. B. Moore-Shedrow, 773-AA;M. Murray, 773-AJ. B. Shaade, 703-FR. C. Tuclcfleld, 773-42AJ. H. Weber, 773-42AJ. C. Williams, 707-FC. R. Wolfe, 773-AD. C. Wood, 704-FJ. E. Young, 773-A

a statistical review of the oxygen data from the gas .../67531/metadc706557/m2/1/high... · a...

Documents