Talk:Uranium trioxide/Archive 3
This is an archive of past discussions about Uranium trioxide. Do not edit the contents of this page. If you wish to start a new discussion or revive an old one, please do so on the current talk page. |
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Badagnani
As in the Depleted uranium article, most of what JamesS added on this topic was found to be misinterpritaions of the referenced literature. --DV8 2XL 23:23, 9 May 2006 (UTC)
- I'm not sure why you didn't just answer the question I asked rather than refer to something else. I read and re-read the citation from the U.S. military website, then the original edit, and found them to correspond closely. Badagnani 23:29, 9 May 2006 (UTC)
- I did answer your question . Are you refering to this ref [1] because it is not avalable due to a 404 error. --DV8 2XL 23:42, 9 May 2006 (UTC)
- I'm sorry to press the issue but, no, you did not answer my question because the "answer" above consists of your opinion that a certain editor misinterpreted certain data. That doesn't answer my question. The link is this one: http://www.deploymentlink.osd.mil/du_library/du_ii/du_ii_refs/n52en017/mr1018_7_chap1.html In your previous blanking of the link, you also did not provide an edit summary other than to say that the edit represented "nonsense." Are you able to explain your deletion? Because I'm interested to know, and not in an ad hominem manner, because I am not interested to discuss other editors, just this point. Badagnani 23:54, 9 May 2006 (UTC)
- The conclusion that UO3 is a signifigant product of burning spent uranium rounds cannot be drawn from that document. Other scienctific sources, clearly say that it is a very minor byproduct. Thus the editor that put it there in fact misinterpreted the document. Thus I answered your question. If indeed you followed the discussion in these pages this issue was hashed over many times.--DV8 2XL 03:10, 10 May 2006 (UTC)
- What other scientific sources say it's a minor byproduct? PaulVT 02:20, 12 May 2006 (UTC)
- The conclusion that UO3 is a signifigant product of burning spent uranium rounds cannot be drawn from that document. Other scienctific sources, clearly say that it is a very minor byproduct. Thus the editor that put it there in fact misinterpreted the document. Thus I answered your question. If indeed you followed the discussion in these pages this issue was hashed over many times.--DV8 2XL 03:10, 10 May 2006 (UTC)
- Many thanks for this. So it is a by-product of DU combustion, then. That is interesting. As only three ways of producing uranium trioxide are now listed here, from what you say a fourth should thus be added: a by-product of the combustion of DU (though, as you say, produced in small amounts relative to the other by-products). Badagnani 03:50, 10 May 2006 (UTC)
That's the whole point, it is nonsense to include it as a source because it is not a significant one. The amounts produced by this route are so small that they do not contribute in any real way to the combustion product profile of DU munitions. If you were a chemist (which you are not) you would understand just why this is so. This was debated at length before. The combustion of this material, from a high kinetic energy impact on various other substances is very, very hard to model in any meaningful way. To state that UO3 is a notable byproduct of such an event is not possible. --DV8 2XL 04:22, 10 May 2006 (UTC)
- Interesting; thank you for this. Maybe you're also not a biologist. Very small amounts of extremely toxic materials (which the MSDS link in this article describes in detail) can be very significant to living systems. I do not think I am incorrect about this. This aside, the statement that there are only three modes of producing uranium trioxide, from what you have said above, is false, and thus this fourth mode of production needs to be added to make the article factual. Badagnani 04:43, 10 May 2006 (UTC)
Then twenty other ways would have to be added as well that could also yield this compound. They are not notable sources and nether is burning DU. The statement in the article is not false because these are the ways the material is produced in significant amounts. Where were you when this was being discussed over the last three or four months? --DV8 2XL 05:06, 10 May 2006 (UTC) Let me put this another way. There is a very much larger amount of uranium oxides from corroding spent rounds (that didn't burn) contributing to the environmental burden that DU is placing on ex-battlefields than any transitory amount of UO3. The real and significant danger is from this material getting in to the water supplies and possibly the plant life through the soil (although for some reason nobody's looked at that angle as yet.) The whole issue of UO3 production from DU munitions came form one editor's very misguided personal crusade to push the idea that it existed as a monomolecular gas. Everyone who looked at his sources agreed that they had been desperately misinterpreted. Continuing to flog this dead horse, and trying to defend this editor's other positions only feeds those that dismiss all criticism of DU munitions as the raving of lunatics. Real facts, and there are more than enough out there, showing that this material can and will do long-term harm to the people and biology of the theaters in which it was used serves the arguments that the use of this stuff must be stopped better. --DV8 2XL 21:39, 10 May 2006 (UTC)
- If you don't believe the 20+ ways should be listed, the "three ways" is still an incorrect statement. Perhaps a statement saying that "there are approximately twenty other ways to produce this, including the combustion of depleted uranium projectiles." That would seem a sensible way to phrase things without making the article too long or cumbersome. Badagnani 21:43, 10 May 2006 (UTC)
- What you are citing is a field manual from the US army, the target of which are military personnel who must protect themselves from DU projectile dust on the battlefield. One should mention that the bioavailability (and thus toxicity) of uranium rises with increased bioavailability. There is one paper here where the authors studied the products from DU armor-breaking projectiles and found the uranyl carbonate (an U(VI) salt) is a product, but no trace of UO_3. I read army manual mentioning UO_3_ as a metaphor for U(VI) in general. Dr Zak 22:17, 10 May 2006 (UTC)
- Thank you for this. I've looked again at the military report and it clearly says "oxides," not "salts." Even the most basic chemist, let alone one in charge of preparing such a report, would certainly know the difference between an "oxide" and a "salt." Are you stating that, due to the one source you present, you believe the military report to be wrong in stating that uranium trioxide is a by-product of the combustion of depleted uranium projectiles? Or is it possible that the uranium trioxide was produced in such a small amount that it was not noted in the study you mention, but was detected by the military scientists in their own tests? There must be an explanation, but yours (the mistaking of a salt for an oxide) does not seem plausible. Badagnani 22:28, 10 May 2006 (UTC)
- It doesn't really matter what exactly is produced during the combustion of DU ammunition. What matters is that whatever is produced ends up in the bloodstream as uranyl carbonate and subsequently causes kidney damage. Dr Zak 22:50, 10 May 2006 (UTC)
You still misunderstand, and I guess it's my fault. Twenty is a convenient number I used to illustrate the futility of making an exhaustive list of every chemical route at every temperature and pressure. This is not just true of this material but of many. The fact is that in the case of burning uranium what ever uranium trioxide is made most likely is going to disappear at those temperatures through the UO3+O2 → U3O8 path anyway. The ones listed are the most important ones, and reflect the common chemistry of this molecule. --DV8 2XL 22:34, 10 May 2006 (UTC)
When I asked DV8 2XL "What other scientific sources say it's a minor byproduct?" above, he accused me of being James, but didn't answer the question. I don't want to get in to this discussion under my usual account, as there seem to be some issues with groupthink going on. (plus DV8 advises "Run for cover" on his userpage.) It shouldn't make any difference who I am. So, are there any sources which actually say that uranium trioxide is a minor byproduct of combustion? 71.132.130.23 06:34, 12 May 2006 (UTC)
Salbu, B. et al. (2005) they simply find only traces of UO3 which is than also not 100% verified. --Stone 09:28, 12 May 2006 (UTC)
Source
- The source states: "The pyrophoric nature of DU is of special relevance to the health effects resulting from DU's use in munitions and armor. Both the impact of a DU penetrator on a target and the burning of DU produce DU dusts or aerosol particles. In addition to resulting in aerosol particles, when DU burns, the high temperatures created act to oxidize uranium metal to a series of complex oxides, predominantly depleted triuranium octaoxide (U3O8), but also depleted uranium dioxide (UO2), and depleted uranium trioxide (UO3) (AEPI, 1995; CHPPM, 1998). Upon weathering, the nonoxidized small particles and surfaces of remaining uranium metal will also slowly oxidize to those three DU oxides over time (CHPPM, 1998)."[2]
This is clearly stated, and thus added to the article as verifiable information about this material. Badagnani 08:49, 12 May 2006 (UTC)
- As Stone pointed out, Salbu, B. et al. (2005) claim only traces of UO3 which is not 100% verified. Your reference is also a secondary source and in fact does not verify the existance of this product. --DV8 2XL 10:26, 12 May 2006 (UTC)
- WP:RS says that secondary sources are more reliable than primary sources. The deploymentlink.osd.mil passage which Badagnani quotes does verify the existence of the combustion product in absolute (100% certainty) terms, and is consistent with the Salbu paper. The correct citation for the deploymentlink.osd.mil source is: Rostker, B. (2000) "Depleted Uranium in the Gulf (II)" Environmental Exposure Reports Tech. Rep. No. 2000179-2 (Washington, DC: Special Assistant for Gulf War Illnesses, Department of Defense).
- That quotation and reference should be added to the article, as should all these other sources which were removed from the article. There is no good reason to exclude any of these useful references, as "Wikipedia is not paper." 171.64.131.83 18:36, 7 July 2006 (UTC)
- Hi James, happy editing from Stanford!
OrgName: Stanford University Network NetRange: 171.64.0.0 - 171.67.255.255 [further lengthy WHOIS information commented out]
- I'll repeat it here for you (it's somewhere in the archives): what you are quoting is a US Army field manual, not a scientific study. The purpose of that source is to provide guidance re. safety for the soldiers; it isn't to be a thorough study of combustion residues. Also, the x-ray data in the Salbu paper is consistent with at most uranyl carbonate. UO3 is nowhere detected. Dr Zak 19:37, 7 July 2006 (UTC)
- On the contrary, it is most certainly not a "field manual." The purpose of the report is stated on its first page:
- Environmental Exposure Reports are reports of what we know today about certain events of the 1990-1991 Gulf War. This particular environmental exposure report focuses on the use of, and exposures to, depleted uranium (DU)....
- -- Bernard Rostker, Special Assistant for Gulf War Illnesses, Department of Defense [3]
- As you know very well from your recent involvement with WP:RS, this source, published by the Office of the Secretary of Defense (osd.mil), is entirely unimpeachable, as are the primary sources which it cites:
- Army Environmental Policy Institute (June, 1995) Health and Environmental Consequences of Depleted Uranium Use in the US Army, Champaign, Illinois, June 1995.
- U.S. Army Center for Health Promotion and Preventive Medicine (1998) Interim Summary, Total Uranium and Isotope Uranium Results, Operation Southern Watch, CHPPM Project No. 47-EM-8111-98.
- Do you claim that those sources (which you removed from the article) are also unscientific? If so, please state your rationale. LossIsNotMore 19:57, 7 July 2006 (UTC)
- On the contrary, it is most certainly not a "field manual." The purpose of the report is stated on its first page:
- Ah, those were removed because they were not used lest the article approach something like the Wikipedia:Spam Event Horizon. Doesn't the edit summary say so? If someone wants to put them back in, that's fine, provided they are actually used to back up a statement made in the article. Dr Zak 20:41, 7 July 2006 (UTC)
Wow, that's a lot of sources removed! I get the sense that someone is trying to prevent Wikipedia users from having certain information. I would never remove sources like that in my own editing. It seems that the "big blue box" at the top of this "discussion" page might not just be reserved for one editor, but for others active on this page as well, if this sort of thing has been going on. Badagnani 20:04, 7 July 2006 (UTC)
And why would you claim something is a field manual if it's not a field manual? This is just too weird. Badagnani 20:05, 7 July 2006 (UTC)
- Of course it's a field manual! When you skip to the conclusions [4] "VI. Lessons Learned and Recommendations" you read in the first sentence: "The Gulf War and its veterans’ subsequent unexplained symptoms have increased awareness of "dirty battlefield" hazards and their possible impacts on the health and readiness of deployed forces." The whole purpose of the publication is how to keep the soldiers out of danger. It certainly isn't an investigative report and doesn't intend to be the last word in analytical chemistry. Dr Zak 20:41, 7 July 2006 (UTC)
- I doubt it was ever actually issued to field personnel, and it isn't listed as a field manual. Do you have any reasons that the primary sources it cites are not authoritative scientific and medical descriptions of the chemistry? LossIsNotMore 20:55, 7 July 2006 (UTC)
- As usual the burden of proof is with the editor that makes an assertion. I haven't read the primary sources that you mention. It's up to you to convince us that UO3 is indeed formed during combustion of uranium. Dr Zak 21:15, 7 July 2006 (UTC)
- I doubt it was ever actually issued to field personnel, and it isn't listed as a field manual. Do you have any reasons that the primary sources it cites are not authoritative scientific and medical descriptions of the chemistry? LossIsNotMore 20:55, 7 July 2006 (UTC)
Don't you all follow Wikipedia's policy of Verifiability? That's the standard. The reference was given, added to the article, then someone removed it. It was verifiable and still is. The proof is in the reference, from a reputable organization with scientists who should know what they're talking about, and backed up with still more references. That's verifiability. And sources don't have to be specifically referred to in the text to be valid to add to an article! That's a ridiculous claim. Badagnani 21:27, 7 July 2006 (UTC)
- Huh? You are misinterpreting the report. The "Environmental Exposure Report" doesn't back up the statement that UO3 is a combustion product, it isn't really concerned what the exact products are, the main focus is the impact on the soldiers and the environment. We would now have to see the references cited in the report to see how they arrived at the conclusion that UO3 is formed. Salbu incidentally tells us that UO3 isn't a combustion product. Dr Zak 21:38, 7 July 2006 (UTC)
- On the contrary, the only evidence against UO3 in Salbu et al. (2005) is a single spectral line, which could easily have been the result of contamination. Several other spectral lines and the spectral contour match UO3. The Environmental Exposure Report, which anyone on the internet can verify, says, "when DU burns, the high temperatures created act to oxidize uranium metal to ... uranium trioxide (UO3)" and cites medical and scientific reports in support of that statement. That is far and away above any reasonable standard, policy or guideline, of inclusion in Wikipedia. If you need a copy of the original primary sources, you can call 1-800-497-6261 and ask for them. But as pointed out above, WP:RS says that secondary sources are considered more reliable than primary sources, so it shouldn't matter unless you discover that Bernard Rostker was incorrectly interpreting those sources. 171.64.131.83 23:00, 7 July 2006 (UTC)
- The exact species formed is a non-issue anyway, since in the body any ingested uranium is converted into uranyl ion, which does the damage. Dr Zak 21:38, 7 July 2006 (UTC)
- On the contrary, if UO3 gas is produced, then some of it will escape into the air before it can condense with other UO3 molecules to form U3O8. Nobody has ever measured the gas products of uranium combustion. So far, only the solid combustion products have been measured. Uranyl absorption from UO3 gas inhalation is immediate, while absorption from U3O8 particles is much slower, because U3O8 is partially soluble and takes months for half of it to dissolve in the lungs. The particulate aerosols diffuse through the air at a different rate than UO3 gas. Therefore, UO3 gas exposure will not always occur simultaneously with particulate oxide exposure. Uranyl ions absorbed by cells from the bloodstream soon become undetectable in the urine, as renal elimination occurs with a half-time of less than two weeks. Since UO3 gas may be encountered without particulates, urine isotope ratio studies which depend on detecting uranium from slowly dissolving uranium oxide particles do not necessarily indicate uranium combustion product inhalation exposure, or the extent of uranyl poisoning. The toxicological profile of uranyl poisoning is dependent on elimination effects, such that a small dose occurring quickly (such as from UO3 gas) will have a different physiological effect than from a larger dose occurring over a longer a period of time (such as from U3O8 particle dissolution in the lungs.) All uranyl poisoning is genotoxic and teratogenic, increasing the probability of chromosome aberrations in white blood cells and birth defects in children. Therefore, empirical measurement of the amount of UO3 gas produced by uranium combustion is necessary for determining the proper medical response to uranium combustion product exposure. Furthermore, karyotyping measurements of chromosome aberrations will proportionally reflect uranyl exposure, in addition to other genetic damage. Unless these questions are addressed, then people will continue to make the mistake of using urine testing to measure exposure instead of karyotyping. 171.64.131.83 22:59, 7 July 2006 (UTC)
It's even worse than I'd suspected. Certain editors fail to find the production of this gas via U combustion, or its health effects, because they're trying very hard NOT to find such. I don't think it would matter what evidence you presented, whether it was 100 studies by the top scientists in the field, they still wouldn't accept it because such a finding might somehow be felt to undermine the public perception of Uranium and its use. And add to this the fact they they hold some sort of veto/censorship power here that is enforced by banning, as well as the continual elimination of sources (up to several dozen at a time, on the incorrecct, groundless basis that sources must be discussed in the article to be given in the Bibliography section) and properly cited, factual statements. Badagnani 23:29, 7 July 2006 (UTC)
Thermodynamics
I have created User:LossIsNotMore/Uranium trioxide, which is a better-formatted, more accurate, and balanced article. I converted all the references to the new <ref> format. I restored the deleted references and the statements they support. I made several dozen corrections in the references (e.g., incorrect volume numbers, missing titles, wrong page numbers and DOIs.) I restored the single-molecule image, and corrected errors in the page. If you agree, please replace Uranium trioxide with it. LossIsNotMore 18:58, 10 July 2006 (UTC)
- That version gives undue prominence to the teratogenic and mutagenic properties when the main target organ of soluble uranium(vi) is the kidneys. Also, the new section on fuel rods isn't really germane to the compound here - last time the issue came up consensus was that is not a bulk chemical and thus should concentrate only on the basic chemistry and reactivity of the compound. Dr Zak 20:59, 10 July 2006 (UTC)
- Kidneys are only vulnerable to acute uranyl exposure, and are completely unharmed (although structurally affected) after years of relatively low-level chronic exposure at levels which cause enough accumulation in cellular nuclei to produce very pronounced genotoxic effects, as well as developmental toxicity in pregnant rats and teratogenicity. The section on fuel rods is not "new" -- it is taken verbatim from the existing article. There is no reference to the term "bulk" in either archive, and no discussion of such limitation of the subject the article, let alone a consensus. Don't you think that teratogenicity is at least as important as ordinary toxicity; if not, why not? LossIsNotMore 21:31, 10 July 2006 (UTC)
- We have a "Health and Safety" section just after the lead paragraph, where the toxicity is addressed. Please James, let's not go again into "uranium trioxide gas", it's not worth it. The paragraph that begins with "During nuclear fuel fabrication" is not backed up at all with the references provided, Chazel (1998) talks about U3O8 particulate matter. It's misinterpreted references, just as it was last time. Dr Zak 21:47, 10 July 2006 (UTC)
- Kidneys are only vulnerable to acute uranyl exposure, and are completely unharmed (although structurally affected) after years of relatively low-level chronic exposure at levels which cause enough accumulation in cellular nuclei to produce very pronounced genotoxic effects, as well as developmental toxicity in pregnant rats and teratogenicity. The section on fuel rods is not "new" -- it is taken verbatim from the existing article. There is no reference to the term "bulk" in either archive, and no discussion of such limitation of the subject the article, let alone a consensus. Don't you think that teratogenicity is at least as important as ordinary toxicity; if not, why not? LossIsNotMore 21:31, 10 July 2006 (UTC)
- Technically you are right that Chazel (1998) doesn't directly support that statement, but I'm not sure it isn't supported by the other references in that paragraph, and most of the sentences are taken from the text of their sources, or closely paraphrased. As for "uranium trioxide gas" this subject is very important for the reasons of determining the appropriate toxicological treatment which has been left unaddressed in the section above. What ever happened to this table?
Thermodynamic energies of uranium oxide gas formation at 2500 K and 1 bar | ||
---|---|---|
Compound | Gibbs free energy of formation |
Proportion as solid of particulate combustion product |
UO(g) | -592 kJ/mol | 0% |
UO2(g) | -1.14 MJ/mol | 25% |
UO3(g) | -1.57 MJ/mol | ? |
U3O8(s) | n/a - produced by condensation and decomposition of UO3(g) |
75% |
from Wanner et al. (2004) Table V.4, p. 98, and Gilchrist et al. (1979) p. ix |
- Didn't Olin offer to do the math for the 2500 Kelvin products? Tri3 23:51, 10 July 2006 (UTC)
- This again. I've never liked this table. First the last column is misleading. My impression from the sorta sketchy reference (have you looked at that Gilchrist reference?) is that it's the solid particulates isolated at room temperature after a combustion reaction. I'm not sure what that has to do with thermodynamic functions, especially since one of the substances is a gas. (Certainly the ΔG's given would not give 3/1.)
- I was hesistant to calculate ΔG's from the data in the Wanner reference because I don't have the patience to find out what the ΔS for O2 and U are at 2500 K (or whatever temperature), which you need for the calculation (since it's formation from O2 and U at that temperature). The numbers that are on the table here are clearly wrong--they were when the person doing the calculation messed up the units. I've been of the opinion through this whole process that calculating ΔG's like this is a little bit sketchy also, because it's not clear that the ΔH and ΔS are temperature independent from the information in the reference particularly over a 2200 K temperature range; there may be data in the primary source, however. It's also never been clear to me what you gain from doing all this anyway since the stoichiometry of each uranium compound (the ratio of U to O) is different, so you are not making a direct comparison, although an equilibrium constant could be calculated. (On related notes, I doubt you would have 1 bar of any uranium product at atmospheric conditions, too.)
- If I were to include a table, I would take the table directly from Wanner and use those numbers as those are citeable, and clearly indicate that those are at 298 K, since it's objective, published scientific data. Hence there are a lot of problems with this table as is. Olin 17:50, 11 July 2006 (UTC)
- Thanks for looking at this again. I'm sorry I can't follow your explanation. How were the units messed up, please? LossIsNotMore 22:12, 11 July 2006 (UTC)
- James--When you did the calculation the last time, you assumed kJ/(mol K) instead of the proper J/(mol K) for the entropy. There's no way that the free energies are in MJ/mol as we discussed some months ago. Olin 12:22, 13 July 2006 (UTC)
- S°m is 310 J·K-1·mol-1 and C°p,m is 65 J·K-1·mol-1 for UO3. What are the Kelvins relative to? LossIsNotMore 07:38, 14 July 2006 (UTC)
- (It's all in the archive, so I'm not going through this again.) Olin 21:02, 18 July 2006 (UTC)
- I am sorry; you are correct. There is a reference to improper conversion in the archive, which assumes that the original unites were in kcal instead of joules, which confused me. My mistake is that I read "kJ" for the actual "J" in Smo values. I have corrected the table above. It has taken me several days to go over this stuff, so I hope you are still interested in doing the calculation, unless I have made another mistake. LossIsNotMore 02:35, 23 July 2006 (UTC)
- Two points: what has the table got to do with the compound uranium trioxide, and what exactly is the point of that table? Dr Zak 18:03, 11 July 2006 (UTC)
- My impression is that it's someone's way of justifying that UO3 is the "most stable form" at the temperature it is burning--i.e., a sneaky way of justifying its existence. Just my impression, though. Olin 18:08, 11 July 2006 (UTC)
- That's what I fear, too. By the way, who has extrapolated the partial pressure of UO3 out to 2500 K? The Ackermann paper goes only to 1700 K and cautions (on p. 354) that "no doubt, the composition of the condensed phase at the temperatures near 1700 °K was different from that near 1300 °K". Total bollocks to insinuate that UO3 is stable at white incandescence! That's where U3O8 decomposes to U2O5. Dr Zak 18:52, 11 July 2006 (UTC)
- Alexander (2005) gives UO3 partial pressures up to 2200 Kelvin (not "°K" by the way.) Moreover, 2500 K is at least 2000 K short of "white incandescence." U3O8 has almost three times the mass of UO3 and seven more atoms, so it's relatively low decomposition point is unsuprising. How much physical chemistry experience have you had, anyway? Dr. Alexander has more than 45 years experience with the chemistry of uranium trioxide gas -- he is a coauthor on Ackermann et al. (1960) -- and has written "I would expect that gaseous UO3 would be the major product of such 'burning' in air.... I don’t know the health hazard of gaseous UO3 but chemically it behaves a lot like WO3 and WO3 is certainly a bad actor. Gaseous UO3 is quite stable and you are correct that upon condensing it would likely become U3O8." (Emphasis added.) Do you have any reason to doubt Dr. Alexander's opinion? LossIsNotMore 22:07, 11 July 2006 (UTC)
- Sorry. I had mixed up Wilson (1961) and Alexander (2005). Dr Zak 01:42, 12 July 2006 (UTC)
- What's the point of the table? I haven't found any other free energies at any other metal oxides in Wikipedia, especially at 2500 K. How would the free energies fit into the text? I just don't see the usefulness of the table now. The vapor pressure is the best number to tell someone how volatile the compound is at these temperatures. Olin 19:59, 24 July 2006 (UTC)
- It shows that in reaction with air at the temperatures which uranium burns, that uranium trioxide gas is the dominant combustion product. A lot of people have been skeptical of that or think it is original research, but this shows it is source-supported. LossIsNotMore 22:43, 24 July 2006 (UTC)
Okay to move the page? LossIsNotMore 04:14, 12 July 2006 (UTC)
- No, James. Dr Zak 04:25, 12 July 2006 (UTC)
- For what reason? Do you still think the secondary source is a field manual? LossIsNotMore 05:11, 12 July 2006 (UTC)
- James, aren't you banned from editing this article? Or have I missed something? Ben 10:52, 12 July 2006 (UTC).
- As you can see from the blue pastel box above, I am "not prevented from discussing or proposing changes on this talk page." LossIsNotMore 23:33, 12 July 2006 (UTC)
- James, aren't you banned from editing this article? Or have I missed something? Ben 10:52, 12 July 2006 (UTC).
- That question has been discussed many times. Dr Zak 13:17, 12 July 2006 (UTC)
- And I have addressed all the issues you have raised. Are there any which you consider insufficiently addressed? Please at least include the improvements of User:LossIsNotMore/Uranium trioxide so that, for example, the wrong volume numbers in the references, and many other things (like categories, for example) are corrected. If there still are any problems, you can edit it from there to address them. LossIsNotMore 23:33, 12 July 2006 (UTC)
- That question has been discussed many times. Dr Zak 13:17, 12 July 2006 (UTC)
Remaining proposed additions
- How 'bout you list the problems in the references here, and then we can fix them? It's too hard to compare the differences in the articles, since they are not in the same spot. Olin 12:22, 13 July 2006 (UTC)
- Ok; first thanks to whomever moved most of it in. Here is what I think remains to be added:
(back left)
- (intro) Uranium trioxide is a product of uranium metal combustion and corrosion. It is a poisonous genotoxin and teratogen in all its forms.
- (Health and safety hazards) During nuclear fuel fabrication or reprocessing stages of a nuclear fuel cycle, it is possible for small particles of uranium oxides including UO3 to escape into the environment.[1] The extent of immediate inhalation intake of uranium oxides is inversely proportional to the size of particles inhaled; uranium oxide gases are absorbed immediately into the bloodstream.[2][3] Urine assay for UO3 exposure can be useful, provided that measurements are made soon after a known acute intake.[4][5] Treatment for UO3 inhalation primarily involves decorporation therapy.[6]
- (Gas phase) Uranium trioxide is produced when uranium burns.[7][8][9] Uranyl ion contamination in uranium oxides has been detected in the residue of depleted uranium munitions fires.[10]
- (Gas phase, appended to its final paragraph) Small pieces of uranium burn at temperatures exceeding 2500 Kelvin.[11]
- ^ Schuenemana RA, Khaskelisa AI, Eastwooda D, van Ooijb WJ, Burggraf LW (2003). "Uranium oxide weathering: spectroscopy and kinetics". Journal of Nuclear Materials. 323: 8–17. doi:10.1016/j.jnucmat.2003.07.003.
{{cite journal}}
: CS1 maint: multiple names: authors list (link) - ^ already in article: <ref name="morrow">
- ^ Chazel V (1998). "Effect of U3O8 specific surface area on in vitro dissolution, biokinetics, and dose coefficients". Radiation Protection Dosimetry. 79: 39–42. full text
- ^ Ansoborlo E (1998). "Exposure implications for uranium aerosols formed at a new laser enrichment facility: application of the ICRP respiratory tract and systemic model". Radiation Protection Dosimetry. 79: 23–27. full text
- ^ Stradling N (2003). "Optimising monitoring regimens for inhaled uranium oxides". Radiation Protection Dosimetry. 105: 109–114. full text
- ^ Stradling GN (2000). "Treatment for Actinide-bearing Industrial Dusts and Aerosols". Radiation Protection Dosimetry. 87: 41–50. abstract, full text
- ^ Rostker, B. (2000) "Depleted Uranium in the Gulf (II)" Environmental Exposure Reports Tech. Rep. No. 2000179-2 (Washington, DC: Special Assistant for Gulf War Illnesses, Department of Defense)
- ^ Army Environmental Policy Institute (June, 1995) Health and Environmental Consequences of Depleted Uranium Use in the US Army, (Champaign, Illinois.)
- ^ U.S. Army Center for Health Promotion and Preventive Medicine (1998) Interim Summary, Total Uranium and Isotope Uranium Results, (Operation Southern Watch) CHPPM Project No. 47-EM-8111-98.
- ^ Salbu, B. et al. (2005) "Oxidation states of uranium in depleted uranium particles from Kuwait," Journal of Environmental Radioactivity, 78, 125–135.
- ^ Mouradian and Baker (1963). "Burning Temperatures of Uranium and Zirconium in Air". Nuclear Science and Engineering. 15: 388–394.
- Rauh EG, Ackermann RJ (1974). "First ionization potentials of some refractory oxide vapors". J Chem Phys. 60: 1396.
What are the problems with those inclusions, if any? LossIsNotMore 07:38, 14 July 2006 (UTC)
Hello? Those four apropo statements are fully supported by their eleven sources, aren't they? LossIsNotMore 09:57, 16 July 2006 (UTC)
- Remarkable bird, the Norwegian Blue, isn't it? Dr Zak 15:44, 16 July 2006 (UTC)
- Please respond to the question. Insulting other editors or dismissing their comments (which are made in all seriousness) is not the way we do things here at Wikipeidia. It doesn't reflect well on you. Badagnani 17:32, 16 July 2006 (UTC)
- Forgive me for being human and having only human patience. These references and the conclusions that they supposedly support have been discussed God knows how often and always been dismissed. Beautiful plumage! Dr Zak 19:04, 16 July 2006 (UTC)
- The few that have been dismissed have been dismissed without reason -- for example, you claimed that the Environmental Exposure Report was somehow inaccurate because it was a "field manual" which was shown to be false. You have not shown how the primary scientific and medical sources which it cites may be inaccurate. Do you or do you not have any remaining objections to the inclusions of those statments and their supporting references? If you do not, then I ask that they be included in the article. Your references to parrots are non sequiturs and disruptive. LossIsNotMore 01:28, 17 July 2006 (UTC)
- We've given you a chance to show you are a serious Wikipedia editor, and have seriousness about editing this article. You have blown this chance with these comments, and unfortunately this undermines the veracity and intent of your previous edits (some of which have subsequently proved to be erroneous). Please answer the questions, because the comments you are making in place of factual comment about the subject make it appear strongly that you don't know this subject well. Badagnani 21:09, 16 July 2006 (UTC)
- Sorry for not stating that I did the changes, but the time log out at my computer is really a problem. But for the Statments mentioned above:
- everything was in and after endless discussions with an edit war and a ban, the statments have been eliminated because see discussion befor. Arguments see archive reactions see archive and so on.........................--Stone 07:48, 17 July 2006 (UTC)
- This "answer" is not satisfactory; please answer the questions regarding the toxicity and teratogenicity of this material, as well as its formation through the combustion of depleted uranium munitions, claims which were and are properly sourced. There is obviously no valid rebuttal, so I believe the properly sourced, verifiable text is going back in the article if there is no objection. Badagnani 12:44, 17 July 2006 (UTC)
- Uranium trioxide is not formed during uranium combustion. Since you think that it is you can present a suitable source. To address point 2, all the sources are not concerned with UO3. It's misinterpreting sources, same as earlier in the year. Dr Zak 13:14, 17 July 2006 (UTC)
- This "answer" is not satisfactory; please answer the questions regarding the toxicity and teratogenicity of this material, as well as its formation through the combustion of depleted uranium munitions, claims which were and are properly sourced. There is obviously no valid rebuttal, so I believe the properly sourced, verifiable text is going back in the article if there is no objection. Badagnani 12:44, 17 July 2006 (UTC)
- Uranium trioxide is formed as a gas during uranium combustion, according to Dr. Carl Alexander, who has more than 45 years of experience in UO3(g) chemistry, being a co-author on Ackermann, et al. (1960) and publishing Alexander (2005) on the subject last year. Would you please discuss this issue directly with Dr. Alexander? His email is alexandc at battelle dot org, and he is easily available by telephone. I have found him to be promptly responsive to inquiries. Would you agree to to speak or correspond directly with Dr. Alexander so that we might resolve this dispute?
- Now, as the unverifiable personal communication of Dr. Alexander is not a suitable source for inclusion in a Wikipedia article (whether or not it will settle this dispute) I remind you that the following suitable sources have been presented:
- Rostker, B. (2000) "Depleted Uranium in the Gulf (II)" Environmental Exposure Reports Tech. Rep. No. 2000179-2 (Washington, DC: Special Assistant for Gulf War Illnesses, Department of Defense), a reliable secondary source which states, "when DU burns, the high temperatures created act to oxidize uranium metal to ... uranium trioxide (UO3)", citing these publications in support:
- Army Environmental Policy Institute (June, 1995) Health and Environmental Consequences of Depleted Uranium Use in the US Army, (Champaign, Illinois) and
- U.S. Army Center for Health Promotion and Preventive Medicine (1998) Interim Summary, Total Uranium and Isotope Uranium Results, (Operation Southern Watch, CHPPM Project No. 47-EM-8111-98.)
- Alexander (2005), which states that UO3 is a volitile gas with substantial partial pressures at the temperatures well below which uranium particles burn.
- The corrected thermodynamic data for uranium oxide gasses in the table in the previous section, From Wanner et al. (2004), which suggests that UO3(g) is even more likely to be produced in quantities relative to the amount of UO2(g) produced at 2500 K than it did before I corrected my J/kJ units mistake.
- Salbu et al. (2005) which detected UO3 modulo a single spectral line, which could have easily been the result of contamination. Salbu et all specifically state that inhaled UO3 should be considered as a health risk.
- Rostker, B. (2000) "Depleted Uranium in the Gulf (II)" Environmental Exposure Reports Tech. Rep. No. 2000179-2 (Washington, DC: Special Assistant for Gulf War Illnesses, Department of Defense), a reliable secondary source which states, "when DU burns, the high temperatures created act to oxidize uranium metal to ... uranium trioxide (UO3)", citing these publications in support:
- You have attempted to impeach some of those sources, but you have not been sucessful at all -- do you think any of your objections to them are still well-founded? Your claim that sources have been misinterpreted is true only to the extent that I misread "J" as "kJ" in the Wanner et al. (2004) thermodynamic tables, and when I corrected that misinterpretation, the evidence became even stronger in my favor. You have not suggested any specific misinterpretations. LossIsNotMore 03:23, 23 July 2006 (UTC)
1 uo3 in nowhere mentioned as comb. prod. of u. Salb finds only weak support in spect.; Alex. Does no combustion only sub. from u308 like Ack.
- Again, Salbu et al. (2005) detected UO3 modulo a single spectral line, which could have easily been the result of contamination. Salbu et all specifically state that inhaled UO3 should be considered as a health risk. LossIsNotMore 03:41, 23 July 2006 (UTC)
2 As there is no oxide gas anywhere mentioned, it will never be inhaled. There is also no Tachion radiation illness within the Tachion artikle! The dust particles are disolved and act than as uranyl ions toxicity see there! Chaz. is not about uo3 but u3o8. Anso. and Strad. do no analytic of what was inhaled so where is the conection to the article.Asob. mentiones only uo3 in not well described mixture, most of the rest is u308 and uo2. strad. OK but as uo3 is a limited danger to people working with uo3 because it is not a combustionproduct of u it is a problem of a minority.
- Firstly, section 2 is only tangentally related to the gas phase. Dr. Alexander does not agree with your assessment -- do you have more or fewer than his 45+ years experience in the subject? Also opposing your point of view is the thermodynamic data, or Salbu et al, or the temperature data in Alexander (2005), which shows substantial partial pressures of UO3(g) at temperatures hundreds of degrees below the combustion temperatures. Any fumes which do not condense with other UO3 molecules remain suspended as disolved gas. As Dr. Alexander writes, "I would expect that gaseous UO3 would be the major product of such 'burning' in air.... I don’t know the health hazard of gaseous UO3 but chemically it behaves a lot like WO3 and WO3 is certainly a bad actor. Gaseous UO3 is quite stable and you are correct that upon condensing it would likely become U3O8" (emphasis added.) You are welcome to discuss your disagreement with Dr. Alexander directly. LossIsNotMore 03:41, 23 July 2006 (UTC)
- Alex is the only source, and he is expecting not measuring anything.With the wiki concept of: The threshold for inclusion in Wikipedia is verifiability, not truth. It would be good to wait for verifiability by experiment not expectations. If he is the only one stating it its original research.
- Note that none of the four sections I've recommended for inclusion specifically state that uranium trioxide gas is produced; only that some form of UO3 is a combustion product. In fact, section two specifically says "small particles" which is taken directly from the abstract of the cited source. LossIsNotMore 10:32, 24 July 2006 (UTC)
3 Wher the heck is this literature from? Even Gmelin and other peer rev papers do not mentione or find uo3 as combustion product so why do they? as rost. states : but also depleted uranium dioxide (UO2), and depleted uranium trioxide (UO3) (AEPI, 1995; CHPPM, 1998). it is not the prime source but only citing something else, the two other sources. Source cycles are not leading anywhere!!
- The literature is an official scientific publication of the US Department of Defense, which has burned more uranium in open air than any other entity, in the thousands upon thousands of tons. Note that the source is a secondary source based on a review of medical and scientific primary sources, and Wikipedia policy considers secondary sources to be more reliable than primary source material. LossIsNotMore 03:41, 23 July 2006 (UTC)
- This secondary source says simply look there to read when you want to know anything about it, not dealing with anything out of the first paper, this makes it not more reliable than primary source. The concept of wikipedia for secondary sources implies, that somebody looked at the results and uses it for his own research, not as a link to a fact the person himself does not look at.
- In this case, the secondary source shows the fact exists in multiple other sources, and the reviewer didn't find anything contradictory when compiling the later report. That gives the secondary source more authority. LossIsNotMore 10:32, 24 July 2006 (UTC)
- If you read the chapter that you are quoting from you'll see that it is actually concerned with the toxicology of uranium in general. The author isn't interested in speciation at all. Dr Zak 00:35, 25 July 2006 (UTC)
- That doesn't change the fact that the statement is credible. It's obvious from the thermodynamics, and Salbu, and Dr. Alexander's opinion. Why do you doubt Dr. Alexander? Will you please speak with him about this? LossIsNotMore 01:46, 25 July 2006 (UTC)
4 But there is no good scientific research done what the uranium at 2500°C looks like and if its really uo3, so it should go to the uranium combustion not a compound which has not the slightest connection to burning uranium. --Stone 17:31, 17 July 2006 (UTC)
- There is no Uranium combustion article. This is the appropriate location for the discussion, because the burning temperature is pertinent to the thermodynamic information of Wanner et al and the partial pressure information of Alexander (2005). LossIsNotMore 03:41, 23 July 2006 (UTC)
- The combination of these two sources is critical, because no research has done about it, if the suggestions are true and even verifiability of the final fact is not possible, so why include it although its against the wikipedia standarts?--Stone 06:17, 24 July 2006 (UTC)
- I really do not understand your question. The section on the gas phase already list partial pressures at various temperatures. What standard are you trying to say including the burning temperature would be against? LossIsNotMore 10:32, 24 July 2006 (UTC)
- What's the purpose of including it? UO3 is a minor component in equilibrium with the other, lower uranium oxides that are formed in a uranium fire. Dr Zak 00:35, 25 July 2006 (UTC)
- For the purpose of including any of this information, search backward on this talk page for the paragraph including the words "some of it will escape into the air". Why do you say that UO3(g) is in equilibrium with the lower oxides? As far as we've been able to tell from the literature, it is only in equilibrium with U3O8, and only if it condenses with other UO3 molecules. LossIsNotMore 01:46, 25 July 2006 (UTC)
- If you read Alexander (2005) you'll see (Table 3) that the solid phase loses oxygen - at 1800 K the O/U ratio is 2.24, quite far away from the nominal 2.67 of stoichiometric U3O8. That happens. As far as "condensing" goes, please note that both Wilson (1961) and Alexander (2005) use the transpiration method, which they couldn't do if they lost a significant amount of mass as non-condensing vapor. Dr Zak 02:33, 25 July 2006 (UTC)
- Okay, so do we agree that a uranium fire will produce, before condensation, both gas and solid particulate products? LossIsNotMore 06:06, 25 July 2006 (UTC)
- NO Give proof! verifiability is the goal! No talk no combination of facts, siple proof.--Stone 06:58, 25 July 2006 (UTC)
- I wasn't asking you if it should be included in the article (and have not proposed any such addition in my recommended additions above.) I was asking Dr Zak if he personally agreed. Since you have answered, though, let me ask you: do you have any reason to doubt Dr. Alexander's opinion on the subject? LossIsNotMore 09:53, 25 July 2006 (UTC)
- I doubt the that there is verifiability for an Wikipedia article! What the truth is is not my problem! ONLY verifiability. I doubt ever opinion even its frm Nobel laureat or God himself, as long its not meeting the criteria of verifiability. If this stuff will not included there is no need for me to discuss further. Usnet is good for this type of discussions, or elswere.--Stone 10:17, 25 July 2006 (UTC)
- The proposed insertions are fully supported by the verifiable sources which they cite -- are they not? None of them claim anything about gas, other than that gas is absorbed directly into the bloodstream if inhaled which is supported by Morrow, already in the article, and for U3O8, another oxide, the other cited reference. LossIsNotMore 12:10, 25 July 2006 (UTC)
C2v UO3
Why are the oxygens huge relative to the uranium in the picture? I know there's debate about how big to make atoms in molecules, but with uranium in the actinides it must be larger than the oxygen.Olin 12:30, 13 July 2006 (UTC)
- My fault. Sorry. Instead of using uranium's van der Waals radius (186 pm), I accidentally used the ionic radius for uranium(VI) (~90 pm). I've fixed the image now. Thanks for noting the problem, Olin. Ben 13:58, 13 July 2006 (UTC).
I thought that ionic bonding was why it's T-shaped and not equilateral trigonal (at least that's what Cotton's book says; I don't understand Pyykkö's Jahn-Teller effect explanation), and so use of the ionic diameter was appropriate. Then again, Cotton says the bonds have been "the subject of much debate." Heh. LossIsNotMore 07:43, 14 July 2006 (UTC)
- The uranium trioxide molecule is covalently bonded. The debate Cotton refers to surrounds the question of which atomic orbitals are involved in the bonding. The T-shape is not related to ions. The diagram you've linked to is illustrating a uranyl ion, UO22+, and how in a crystal structure, not all oxygens are equidistant from the uranium(VI). It is not a diagram of a molecule of UO3. I don't understand the Jahn-Teller effect either, but it doesn't matter - I can still draw a molecule based on the bond lengths and angles found by Pyykkö!
- I should read through Pyykkö's paper again to see what degeneracy is lifted by distortion from D3h to C2v. Dr Zak 22:54, 16 July 2006 (UTC)
- Thanks for fixing this! Olin 12:33, 17 July 2006 (UTC)
Is a source really needed for "fire makes gas"?
Fire#Science of fire starts, "A flame is an exothermic, self-sustaining, oxidizing chemical reaction producing energy and glowing gas, of which a very small portion is plasma." (emphasis added) When I asked Dr Zak whether he agreed that uranium fires produce both gas and solid products, Stone suggested that proof would be required. Is there any evidence that uranium fires do not produce gas, like every other kind of fire?
Again, I point out that my four proposed additions above to not explicitly state that gas is produced. However, the implication of puting some of them in the "Gas phase" section is understood, but as it involves no explicit claims, I submit that since all fires produce gas, and since UO3 is the thremodynamically most likely combustion product, and its proportion seems to agree with the amount of solid U3O8 which eventually forms from decomposition after condensation, that their inclusion in that section is justified. LossIsNotMore 03:04, 27 July 2006 (UTC)
- "Yes" to what? That a source is needed? Indeed it is, per the carefully worded "No Original Research" policy that exists primarily to keep the kooks out of articles. Dr Zak 19:36, 27 July 2006 (UTC)
- But the proposed insertions above dont say that a gas is produced. I just wonder whether the overwhelming evidence from the DoD, thermodynamics, etc., justifies putting relevant -- and fully sourced -- facts from Rostker, Salbu, and Mouradian and Baker in the "Gas phase" section. There is certainly nothing prohibiting that in WP:NOR. Is there any reason not to? It feels right to me. If I am a kook then Dr. Alexander is, too. Has anyone else bothered to speak with or email Dr. Alexander yet? LossIsNotMore 19:55, 27 July 2006 (UTC)
- What exactly is the point that you wish to drive home? That UO3 is in equilibrium with U3O8? The article says so already? Whatever you say, please remember that the UO3 vapor pressure was measured by the transport method and that at lower temperature UO3 was converted back quantitatively to U3O8. Dr Zak 20:08, 27 July 2006 (UTC)
- Just because something is thermodynamically stable, doesn't mean it is formed. Graphite is more thermodynamically stable than diamond, but diamond does not convert to graphite because it is impossible due to the kinetics of such rearrangement. The fact that UO3(g) is low in energy does not imply its existence.
- On the subject of Dr Alexander, using his email as a basis for writing the article is original research. What he writes in emails does not go through the pier review process and shouldn't be used.
- We shouldn't make claims along the lines of:
- all fires produce gas
- UO3(g) is more thermodynamically stable than UO2(g), UO(g) and U(g) + O2(g)
- something to do with proportions and U3O8
- therefore loads of UO3(g) is produced
- We shouldn't make claims along the lines of:
- Such reasoning is tenuous and should generally be considered to be original research. While some editors may consider the first three bullet points good justification for the conclusion, I do not feel that this necessarily follows logically.
- I am not against the idea of UO3(g) in principle, I don't have any financial or other affiliations with the military or industry. I'm just a student. But I feel strongly that Wikipedia editors should refrain from publicising their own obsessions. I use WP for reference. If I want to find out about uranium trioxide, I do not want a load of possibly false information about uranium trioxide gas that has been cobbled together from sources all over the place, making statements that no individual source actually claims. Can't we just stick to re-writing what others have published, without trying to interpolate all the time?
- If a study is published in a proper, pier-reviewed scientific journal, where the authors burn uranium and measure the amount of any UO3(g) produced, then we can definitely write about it. But until then, let's simply not get into the habit of making spurious claims. Doing so damages the reputation of Wikipedia and provides false information to its readers.
- Perfect arguments, kindly verbalized, I like it Ben! I always had the problem to find the right words to end the discussion, maybe yours are good enough!--Stone 06:31, 28 July 2006 (UTC)
Gah. "Uranium trioxide is produced when uranium burns." It's well-sourced, obvious from the thermodynamics, and supported by Salbu's emperical evidence. That's the only point I'm "trying to drive home." And it's something that an encyclopedia article ought to say about uranium trioxide.
All I'm trying to ask is whether the circumstantial evidence justifies putting that sourced statement in the "Gas phase" section. Again, for the umteenth time, I'm not trying to say that the gas is produced, I'm not proposing citing Dr. Alexander's email in the article, and I haven't written anything which might imply that I am. LossIsNotMore 19:51, 28 July 2006 (UTC)
- Under many circumstances burning aluminum powder in air produces no evolved gas as the reaction product (corundum) is refractory and do not vaporize even at 2500C. My point is that it is not obvious that flames produce gas, even if it seems intuitively so. Therefore it is reasonable to ask for citation. zowie 21:07, 28 July 2006 (UTC)
- What happens to aluminum oxide molecules which escape the plume before condensing on other molecules or particles? Is there any way to quantify those? LossIsNotMore 10:08, 29 July 2006 (UTC)
- I would add that the vapor pressure is in the article (8.1 mbar at 2500 °C). That is a source-supported amount of UO3(g) at that temperature in the atmosphere. It would indicate that at that temperature you are way below the boiling point of UO3, and that there must be significant solid uranium compound around. (Water has about the same partial pressure at 5 °C (~6 torr)! Do we say that there is significant water vapor in air at 5°C? Does the Wikipedia article on water dwell on that for paragraphs on end?)
- The triuranium octaoxide article states "uranium trioxide (UO3) loses oxygen at temperatures above 500°C and is reduced to U3O8." (Albeit that article doesn't have any references in it...) Under boiling point, it states "decomposes to UO2 at 1300 °C", and UO2 melts at 3120 K (in the uranium dioxide article).
- My conclusion from that data (all perfectly valid thermodynamic data) is that at 2500 °C mostly you have solid UO2 and a trace of UO3 gas, again about as much in pressure as there is water at 5 °C.
- It may very well be that in an excess of oxygen that trace gas is UO3. But I don't think it's worth cramming that point in the article. Furthermore, that vapor presure is miniscule at room temperature; particulate U3O8 may be breathed in, for sure, but the gas? Olin 21:39, 28 July 2006 (UTC)
- The burning temperature, from Mouradian and Baker page 392, is at a minimum 2500 Kelvin (not °C), and significantly more for micron-scale particles. And the vapor pressure rises rapidly:
Temperature (K) |
Volatility of UO3(g) (mbar) |
---|---|
1250 | 10-5 |
1670 | 0.1 |
1800 | 0.34 |
2000 | 1.9 |
2200 | 8.1 |
sources: Ackermann et al. (1956) and Alexander (2005), Table 6 |
- Again, I'm not suggesting saying that the gas is produced, let alone going on for "paragraphs on end," in the article. I'm just trying to ask whether the statement that the substance is produced in a fire is reasonable to include in the "Gas phase" section.
- As for decomposition into U3O8, we know it occurs in UO3(s) but the equilibrium indicates that it doesn't occur in UO3(g). There is simply nowhere to obtain the other two uraniums, for one thing, so the gas can't decompose into a larger molecule no matter how hot it gets.
- Following the same analogy with water, would it be reasonable to state that water is produced in several combustion reactions in Water#Steam (if there was such a subsection)? LossIsNotMore 11:36, 29 July 2006 (UTC)
- That may be the most appalling extrapolation of data I've ever seen. It's an empirical correlation, and it fits up to 2500 degC. In any fit the error increases the farther from the data your are. I could care less what your R or R2 is, so don't even try. It's also as original a bit of research as I've seen.
- I find the juxtaposition of the statements "I'm not suggesting saying that the gas is produced" and "reasonable to include in the 'Gas phase' section" utterly confusing. Paradoxical, even.
- It never was much in the gas phase, so it doesn't have to "obtain" uranium atoms from anywhere.
- I found a paper that has a phase diagram for uranium-oxygen system. I'm going to request it as I don't have access. It's called "p Versus T phase diagram of the uranium-oxygen system" (Yu. V. Levinskii, Atomic Energy, Volume 37, Number 4, October 1974, 1075 - 1076). If anyone has access to that, I'd love to see it and see what the "most thermodynamically stable state" is at 2500 K or degC or whatever. Then maybe I'll retire from this silliness.) Olin 23:58, 29 July 2006 (UTC)
- PS It's interesting that the Mouradian and Baker reference says "theortetical burning temperature." I'd love to see the paper in context to see what that means. Olin 00:01, 30 July 2006 (UTC)
- Well, I understand that I probably shouldn't claim an adjusted R2 > 0.99 since the underlying data is only two significant digits, but as luck would have it they fit amazingly well. I fully understand that the confidence interval should be correspondingly divergent, and perhaps if I add random noise to the data I can get a more accurate R2 and a resulting more reliable confidence interval. I wasn't trying to appall anyone.
- Oh, and as for the theoretical-experimental distinction for the burning temperature, see Figure 6 on page 392 of Mouradian and Baker. Keep in mind that it is for foil, and not spherical particles. After peircing armor, the "self-sharpening" process "liquifies" uranium which fragments into a "shower" of "molten droplets" per the DoD descriptions of the tests against tank armor. LossIsNotMore 18:32, 31 July 2006 (UTC)
- Does "theoretical" mean "fitted data"? And there must be some text to explain that figure--you're just putting it there out of context means nothing to anyone. As for your fit, there clearly is not enough curvature in the data you have to extrapolate it out as far as you have. Do you really think that your data from 0.00001 to 8.1 mbar is extrapolatable to 500 mbar? To 50x your highest data point? Olin 01:30, 1 August 2006 (UTC)
- No, "theoretical" means "according to M&B's theory of burning with a layer of oxygen-depleted air surrounding the metal" which most of the beginning of the paper describes. Yes, I know the fit is horrible and I promise to redo it. TableCurve has an "add noise" option but it only works in autoregressive modeling and prediction, and I can't even get that to extrapolate beyond the first and last data points for some reason. I spent almost half the day trying to get that Russian Atomic Energy paper: Stanford doesn't have it, but the University of California system does, and the reference librarians can click on the link above and go stright to the PDF. However, the UC Extension campuses in Sunnyvale and Cupertino both have IP addresses assigned to SBC instead of UC, so Springer wouldn't give up the PDF. Then my daughter had to go swimming and I couldn't drive to Berkeley or Santa Cruz. Maybe tomorrow. How long is your ILL supposed to take? LossIsNotMore 07:13, 1 August 2006 (UTC)
- Okay, I got AR working, but it provides much the same extrapolation without confidence intervals. I'm adding noise manually. With a 95% prediction interval of (42.0, 47.1) at 2500 K, it is (429, 436.5) at 3000 K. That's not much more width at all. Those linear exponential intervals don't diverge anything like the logistic sigmoids I'm used to. LossIsNotMore 08:13, 1 August 2006 (UTC)
- The graph is fixed. After experimenting with adding random data (as well as replacing the five points with ten for five intervals of various widths at each original point) it became clear that the exponential shown was the best overall fit, which is good because it isn't computed in the log domain, so it has legitimate 95% prediction intervals. It also shows higher vapor pressures approaching 1 atm at the likely burning temperatures. LossIsNotMore 04:39, 2 August 2006 (UTC)
- What you've shown, J, is clever maths, but I feel it would be more suitably sited on your own website, because it's towards the wrong end of the grey area between plotting established data and coming up with your own predictions (therefore not allowed on WP due to NOR). We could write a section in the article along the lines of:
- "Some campaigners (i.e. James and others) have raised objections to the use of DU bullets, concerned that burning uranium can form UO3(g) in quantities great enough to be inhaled by bystanders (most likely soldiers in the Gulf War). Due to several research papers (here you insert links to Morrow etc), they expect that any UO3(g) entering a human body would cause great damage to a variety of organs (all those different kinds of toxicity (e.g. nephrotoxicity) and birth defect formation), and exposure to such toxins may be a cause of Gulf War Syndrome."
- I don't know how far other editors are prepared to go towards writing James' entire CV in the article(!), but perhaps a brief mention (with external links to the original research James has spent lots of time doing here) of the controversy surrounding uranium trioxide in particular is appropriate. After all, other editors (who didn't appear to be James bearing a pseudonym, such as Badagnani) have written on this talk page expressing concern at the lack of mention of controversy. On the other hand, as far as I'm aware, James' concern about UO3 specifically is quite a niche view, although concern about depleted uranium is much more widespread. Perhaps some editors feel such minority views should not receive such coverage, lacking notability, but if it James becomes a sort of Erin Brockovich, there'll be films about how we cast out his views!
- I've gone off on a tangent slightly, but my point is this: nice work James, but don't put that graph in the article! Until someone does an experiment and finds some data points near your lines, your graph is simply not science.
- No, I've learned my lesson; I don't want anything like that included. I'm just arguing for the four inclusions above, and after that I promise to be quiet here. At least until there is a ruling on my NRC petitions, which will have the authority of the US government behind them. I've already had one granted in part, but not in a way that would make any difference in this article (maybe it would over on depleted uranium, but it would be trivial and the changes I'm asking for here at UO3 are a lot more important.) The new NRC petition asks the NRC to require the uranium munitions licensees to measure the gas combustion products and the amount of chromosome abberations caused by combustion product inhalation, and based on how the last 10 CFR 2.206 petition went, I think this revised one has a very good chance. In large part it's because of Dr. Alexander's help. If it wasn't for the tough arguments here on Wikipedia, I would never even have known Dr. Alexander still existed, let alone obtained his agreement to help with my latest petition. I hope nothing so interesting happens that anyone ever wants to make a movie about me. I'd be satisfied if the ABC News reporter who calls me every few months after arguments occur on the RadSafe mailing list ever writes a story.
- Anyway, we're getting the Soviet p-versus-T diagram soon, and I'm told it goes up to 3000 °C for UO2.6(g). That should help a lot. Although, for this article, we won't be able to use it because it doesn't explicitly describe UO3 behavior. LossIsNotMore 03:35, 3 August 2006 (UTC)
Levinskii74.pdf
Levinskii, Y.V. (1974) "p-versus-T Phase Diagram of the Uranium-Oxygen System" Atomic Energy 37(4):1075-6. Please correct me if I'm wrong, but that looks pretty clearly like UO3 hits 1 atm at about 1300 °C.
Now would someone please add the DoD Environmental Exposure Report statement and all four of the #Remaining proposed additions? LossIsNotMore 23:07, 5 August 2006 (UTC)
- Never mind the fact that at higher temps. there are other species that are more stable and their phase diagrams don't specify which gas is around. Olin 17:10, 6 August 2006 (UTC)
- Would "a large fraction of the gas product" be supported? 66.122.34.11 23:19, 6 August 2006 (UTC)
- G stands for gas but what gas is not given. My view of the graphs is that at 1300 or whatever the UO3 is transformed into U3O8 and the pressure of Oxygen produced by this reaction exceedes 1 atm. While looking at the third diagramm tit looks like all Uraniumoxides are transformed into UO2 and than it sublimes at temperatures above 1800 and 2000. As there is no direct UO3 mentioned it gives a perfect insight that uo3 is not stable at elevated temperatures and U3O8 and UO2 are the only stable formes at elevated temperatures. --Stone 11:26, 7 August 2006 (UTC)
- Stone, why do you think U3O8 is stable above 1500 °C? LossIsNotMore 18:11, 7 August 2006 (UTC)
- I agree with Stone--If UO2 disproportionated to UO3 and U or UO or U3O8, that would have to be on the phase digram--it wouldn't make sense otherwise because of stoichiometry. And it wouldn't really make sense for UO3 to be stable at low T, then not at intermediate T, and the stable again at high T. Olin 14:00, 7 August 2006 (UTC)
- Well then, why do you think U3O8 is stable above 1500 °C? I can't find anything supporting that, and there have been multiple contradictions of it. LossIsNotMore 16:36, 9 August 2006 (UTC)
- I don't think it is--I think UO2 is, as I've said on this page before, and is indicated on the phase diagram, and in the appropriate articles in wikipedia. Olin 17:47, 9 August 2006 (UTC)
- Then how do you explain that the pressure for UO3(g) is strictly greater than any plot of the UO2 pressure, within the rectangle of the p-vs-T diagram, along with the corresponding enthalpies we've been discussing? LossIsNotMore 18:29, 9 August 2006 (UTC)
- I understand what you're saying about the enthalpies or free energies--I really do. But I think that's not obtainable from the phase diagram. (To be honest, it wasn't the clarifying find I'd hope it would have been, since none of the gases are specified on the phase diagram.) The UO3G I think has a missing comma and should be UO3,g.
- From a naive point of view, it looks like by figure 2 that everything over a certain temperature is UO2 at least in the solid or liquid phase. It makes you think that UO2 is the most stable form of uranium in any proportion of oxygen above a certain temp, and that maybe it boils off. But I'm speculating.
- I think some of the "G" on the diagram must be O2. For example, on Figure 2a as you increase the proportion of oxygen, you go from uranium liquid (this must be L1, since there's no oxygen), to L1 + UO2(s), to UO2(s) (all of the uranium must be UO2 now) to UO2 + gas. It would make sense that that gas is O2 or some mixture. But I'm not sure.
- I am open to that fact that there is some UO3(g)--the vapor pressure data says that--but not a lot of it. Olin 20:50, 9 August 2006 (UTC)
Moreover, the temperatures are useless because for practical use we would need the N-O-U system, and it is complicated because uranium reacts with N2 at about 700 °C. LossIsNotMore 17:02, 7 August 2006 (UTC)
O3U
What was the objection against including NIST nomenclature? LossIsNotMore 18:05, 7 August 2006 (UTC)
- Read archive.--Stone 06:45, 8 August 2006 (UTC)
- Archive says editors are unfamiliar with the alternative usage. Wikipedia guidelines say include comprehensive information. I suppose there might be some editors who think that a major source of high-precision numeric information about a large number of compounds from the US government might be too esoteric to fit within their abridged idea of comprehensivity. LossIsNotMore 10:30, 8 August 2006 (UTC)
- I think this argument should be part of a wider one. What James refers to as NIST nomenclature is more generally known as the Hill system. If we're going to have both UO3 and O3U given as the chemical formula of uranium trioxide, it should be part of a wider move to include Hill system formulae in all chemical compound articles, or at least for inorganic compounds. James, I think you should pay a visit to the Wikiproject on Chemistry to request this.
NIST nomenclature is more generally known as the Hill system I never had any contact with strange things like O3U and I do chemistry for several years. Where does this NIST stuff come from and why they dont use the system used in every literature and book I know? But does anybody really need O3U? But in the list of other names we can put this formula.--Stone 15:13, 8 August 2006 (UTC)
- It's a little obscure, I know! I've come across the Hill system on Webelements. I think it's mostly used in cheminformatics to simplify database searching. Personally, I don't think the system is particularly noteworthy, but James' logic is sound - WP does aim for comprehensive coverage. Raising the issue at the Chemistry Wikiproject should help us decide one way or the other.
- Actually, I've had a course on chem info science; the Hill system is used, but more in an index if you are looking up a compound. That is, it's a way of ordering compounds, not really a nomenclature system. So if you had 9000 compounds in a list, you would have some systematic way of finding the one you wanted. (There are actually a bunch of these systems.)
- It's fairly standard in chemistry, however, to put the more electronegative element last (with notable exceptions like NH3.) Most chemists would look at O3U and say, "huh?" Which is why Ben, Stone, and I are grumbling. Olin 17:54, 9 August 2006 (UTC)
- Fair enough. How about the link to NIST's page on UO3? LossIsNotMore 18:29, 9 August 2006 (UTC)
- You want it there because it says "Gas phase ion energetics data" and has a psuedo-Lewis structure, eh? NIST does good stuff--they are the standard in thermochemical data. Where would the reference go? Olin 21:14, 9 August 2006 (UTC)
- I want it in the article because it has a lot of good information. I didn't even know about the gas phase ion energetics data until I read your mention of it, just now. Honestly, I must have seen that but forgot about it because I don't know what to do with the EA and IE data. NIST gets the structure angles right, but also has correct structure diagrams for equilateral trigonal compounds. In answer to your question, I think it should go right after reference [9] in the #Remaining proposed additions which I hope you will support now given your most recent statement in the section above.
Carter and Stewart
Title Inhaled particles : proceedings of an international symposium / organized by the British Occupational Hygiene Society. Publisher Surrey : Unwin Brothers Ltd., 1971- Description v. : ill. ; 26 cm. Publishing History 3 (14-23 Sept. 1970)- ISSN 0301-1577 LOCATION UC Berkeley PubHealth RC773 .I53 1970(3)
- But I can't James; it just doesn't make a consistent, complete picture from the data and from the references. It's not a matter of my supporting it, it's about the literature being consistent. The vapor pressure I have no problem with. Combustion product, no. (I suspect that article will be about solid particulates and not gas, given the title of the journal, btw...) Olin 22:20, 9 August 2006 (UTC)
- "fume (fyūm) noun,
- "1. Vapor, gas, or smoke, especially if irritating, harmful, or strong.
- "2. A strong or acrid odor.
- "3. A state of resentment or vexation." (emphasis added)
- Well, I'm not fuming (at least in terms of def'n 3). I don't have to convince you, I only need to convince the NRC, and they have to abide by 18 USC 1001. LossIsNotMore 23:22, 9 August 2006 (UTC)
JM23 08:38, 17 August 2006 (UTC)
- While interesting on a technical note, this means very little as the vapor pressure of UO3 at 2100C is only 34Pa, or .000335 atmospheres! A meaningless amount that condenses very rapidly back into a solid form. There is more free Neon and Methane in the atmosphere at STP than there could ever be UO3 at degrees commonly found inside a BOF. Tell James to drop it. Torturous Devastating Cudgel 15:46, 17 August 2006 (UTC)
- It does, however, prove the point about the gas being a major combustion product, which seems to occupy 95% of this page. How can you say how fast it condenses? Ordinary clouds go in and out of vapor phase all the time, far below water's boiling point. If you want to say something about the condensation, you need sources. 66.167.206.57 02:24, 19 August 2006 (UTC)
- Um, if it's near the vaporization of the metal, it's not at the 2100 K or degC or whatever James cites. The wiki page says that uranium boils at 4404 K, which is vaporization. That's a huge difference in temperature! Also, what does this say about UO3? The gas is not identified. Does the paper identify the vapor as UO3? Interesting that there are a lot of talk of aerosols in this out-of-context segment, huh? (Good point TDC, about the ~0.5 mg per liter of air.) Olin 15:50, 19 August 2006 (UTC)
- They aren't igniting at the vaporization point, they are burning at temperatures which reach 4400 K as the particles get smaller. Levinskii (1974) says that UO3 has the greatest partial pressure of all the oxide gasses. Ackermann et al. (1956) and Alexander (2005) both say the partial pressure of the trioxide increases with temperature, so it's not unexpected that such small particles, which are, by the way, exactly what DU penetrator ordance spray into after peircing armor, produce even more gas than from solid metal fires. What's the next likely alternative hypothesis other than trioxide being a major combustion product? We know it's not forming all UO2 because that's stable and comprises only 25% of the eventual product, not ~50%. There aren't any other oxides likely to form. The talk about aerosols makes it completely clear that there is a vapor component which condenses into a fume component, seperate from the particulate aerosols. The full report is here for all the context you want. The page above is clearly the conclusions. 24.6.173.156 23:50, 20 August 2006 (UTC)
- Thanks, and for the last time James: IT IS NOT A MAJOR COMBUSTION PRODUCT!!!'. Torturous Devastating Cudgel 16:54, 19 August 2006 (UTC)
- Are there any sources at all which agree with that opinion? No, there aren't. 24.6.173.156 23:50, 20 August 2006 (UTC)
- <<Yawn>> No need to be in an edit war with a banned author, especially one that violated his ban. I've probably ruined my reputation here because if it. Any way, best of luck. Bye, now! Olin 00:22, 21 August 2006 (UTC)
- As usual, there is never any reason ever to be rude here at Wikipedia. He is not the only person who is deeply interested in getting to the bottom of this issue of where all the particles go when this material is used in the "real world" (i.e. the extensive use in combat over the past decade) not in the lab. I'm sure you agree that much of what he says makes sense; in fact over a half dozen times he's pointed out things that other editors didn't realize before. This dialogue is without doubt a positive thing, as it's bringing minds together to determine the veracity of these issues. Let's not return to the "bad old days" when people were extremely rude and dismissive here, but continue evaluating the evidence and sources in a respectful and scholarly way. Badagnani 00:43, 21 August 2006 (UTC)
- James' use, or should I say misuse, of technical data to push a point has gone to the levelof ludicrous. If he wants wants to fight the crusade that the use of depelted uranium munitions is sending vast quantities of uranium gas into the atmosphere, this is not the place to do it. There was a reason his FOIA was rejected, and a reason that any Wikipeida with even the most rudimentary knowledge of chemistry found his claims to be not valid. James is not a chemist or an engineer, and every one who does has some knowledge has told him repeatedly that he is embarrasing himself by bringup these points. He does not understand the material he is presenting. Torturous Devastating Cudgel 01:46, 21 August 2006 (UTC)
- TDC, would you be willing to phone and/or email Dr. Carl Alexander at Battelle and speak with him about this? He has 45 years of experience on the topic, and I've spoken with him on multiple occasions and exchanged emails over a period of months. I have no doubt that he will convince you of my longstanding position, if, you know, you really want to know the answer and take the trouble to call or email. By the way, I never said "vast quanities" -- if you look at the Talk:Depleted uranium archives from around January or February, if I recall correctly, I was guessing 3%-12% of the metal burned ended up as uncondensed gas. Is that vast? Anyway, I've put in more than just one FOIA request, and so far only one has been rejected (and they seem to have lost my appeal!) The NRC is still mulling over the most recent petition, and they granted the one from last year (in part), so for a layman, I think I have a pretty good record. LossIsNotMore 11:40, 31 August 2006 (UTC)
- Notwithstanding the fact that the Army publication cited earlier states unequivocally that Uranium trioxide is produced during battlefield combustion of DU ammunition, what gases are produced during such pyrophoric explosions when tanks or other vehicles are destroyed with such ammunition? None? Or is it all particulate? This is what needs to be determined? I believe the answer is somewhere in between what you are are "sure" of, and what James is "sure" of. The thing is, the Army should have (and apparently did) determine all of this before putting the material into such wide use in this context, otherwise their official publication would not have stated that Uranium trioxide was produced during such use of depleted uranium ammunition. Badagnani 02:14, 21 August 2006 (UTC)
Jette et al. (1989)
- "Review of Experimental Studies on Airborne Release From Depleted Uranium Munitions. Jette et al. (August 1989) reviewed the published information available on the characteristics of the DU particles suspended during testing (firing of kinetic energy rounds against hard targets, burn tests during hazard classification of rounds prior to deployment) of the munitions and one study on the characteristics of the aerosols from the explosive ejection of molten metal droplets. Many studies have been performed on the DU particles formed by the impact of penetrators against hard targets (Gilchrist and Nicola, January 1979; Glissmeyer and Mishima, November 1979; Chambers et al., October 1982; Sutter et al., January 1985; Wilsey and Bloore, May 1989; Parkhurst et al., April 1990; Jette, Mishima and Hadlock, August 1990). Generally, a substantial portion of the mass of DU in the penetrator becomes airborne by the impact against hard targets (armor) of sufficient thickness to expend most of the energy of the kinetic round (up to 80%). The size of the airborne material is very fine with fractions in the 10 μm AED and less range of 0.34 to 1.0. The airborne materials are predominantly U3O8. Up to 50% of the particles in the respirable fraction may be "D" class (dissolution halftime <10 days)."
- -- DOE-HDBK-3010-94 (emphasis added) page 4-40 (PDF page 130) commenting on Jette, S.J., J.A. Glissmeyer, J. Mishima, D.J. Sherwood and R.E. Williford (August 1989) Potential Aerosolization (Airborne Suspension) of Depleted Uranium During Test Firings, PNL-7137 Informal Letter Report, Pacific Northwest Laboratory, Richland, WA 99352.
More people who imply, against all evidence, that U3O8 is stable above 1300 °C. There ought to be a name for such people: wrong. Dr. Alexander knows what is actually happening, and if you are reading this, you probably do to. Such a disgusting travesty, not bothering to measure the gas products, and then trying to pass off urine tests. LossIsNotMore 04:17, 11 August 2006 (UTC)
- A simple peer-reviewed statement, that says, "Uranium trioxide gas is evolved in uranium combustion. [insert cited source here]" will suffice. No phone calls necessary.Olin 21:30, 11 September 2006 (UTC)
Bond valence parameters
This is more about caluculating the parameters than giving them for uranium(VI) oxide. Could this be condensed to "Bond valence parameters have been used to give typically uranium-oxygen bond distances in different oxidation states," and then the table given? Can the references about bond valence parameters be moved to bond valence, which has no references? Might it be moved to uranate, where a comparison between oxidation states is more appropriate?Olin 16:19, 19 August 2006 (UTC)
Discussion from Wikipedia talk:WikiProject Chemistry
(continued from Wikipedia talk:WikiProject Chemistry#Uranium)
There is no question that the combustion of uranium results in the production of uranium trioxide gas, for the following reasons:
- Dr. Carl Alexander at Battelle, with over 45 years of experience on the subject (he was a coauthor of the Ackermann et al (1960) paper on UO3 gas, and the sole author of another pertinent paper last year) agrees that it does. You can reach Dr. Alexander at +1-614-424-5233 or at the email address obscurely indicated in the "From:" line below. Here is a copy of his first email to me:
Subject: RE: uranium combustion produces how much UO3(g)? Date: Thu, 20 Apr 2006 16:31:15 -0400 From: Alexander, Carl A (alexandc at BATTELLE dot ORG) To: James Salsman (james at bovik dot org) I would expect that gaseous UO3 would be the major product of such “burning” in air. I consulted and reviewed Wendell Wilson’s paper prior to publication so I am familiar with it although I haven’t seen it in a good many years. I don’t know the health hazard of gaseous UO3 but chemically it behaves a lot like WO3 and WO3 is certainly a bad actor. Gaseous UO3 is quite stable and you are correct that upon condensing it would likely become U3O8. -----Original Message----- From: James Salsman Sent: Thursday, April 20, 2006 4:11 PM To: Alexander, Carl A Subject: uranium combustion produces how much UO3(g)? Dear Dr. Alexander: Thank you for publishing your paper, "Volatilization of urania under strongly oxidizing conditions," which I recently read with great interest. I have been trying to determine the amount of UO3(g) produced from combustion of uranium. I have recently been corresponding with the famous coordination chemist Prof. Simon Cotton, who suggested that I contact you with my question. Depleted uranium munitions such as those used for 20-30 mm and larger antitank ordnance are incendiary due to the pyrophoric nature of uranium. More than 30% of such bullets' uranium metal burns in air when they are fired against hard targets. It seems that the burning temperature should usually be above 2500 Kelvin, because the bullets are described as fragmenting into a spray of tiny particles as they pass through armor. (Mouradian and Baker (1963) "Burning Temperatures of Uranium and Zirconium in Air," Nuclear Science and Engineering, vol. 15, pp. 388-394.) Inhalation of uranium combustion fumes is suspected in major illnesses reported in veterans and civilians of the February, 1991 Gulf War. However, none of the people responsible for determining the health hazards has yet reported measurements of the gas vapors produced, only the particulate aerosol fumes, which are described as 25% UO2 and 75% U3O8 (Gilchrist R.L., et al. (1979) "Characterization of Airborne Uranium from Test Firings of XM774 Ammunition," Technical report no. PNL-2944 Richland, WA: Battelle Pacific Northwest Laboratory.) Based on the thermodynamic formation energy data I have been able to find (H. Wanner and I. Forest, eds. (2004) Chemical Thermodynamics of Uranium (Paris: OECD and French Nuclear Energy Agency) http://www.nea.fr/html/dbtdb/pubs/uranium.pdf -- see table V.4 on p. 98) it seems like production of UO3 would be much more likely than UO2 or U3O8. Moreover, condensation and subsequent decomposition of UO3(g) can explain the U3O8(s) product: see Wilson, W.B. (1961) "High-Pressure High-Temperature Investigation of the Uranium-Oxygen System," Journal of Inorganic Nuclear Chemistry, vol. 19, pp. 212-222, at the bottom of p. 213. If there are substantial amounts of UO3(g) produced in uranium fires, that could explain discrepancies in both troop exposure patterns and the solubility and resulting pharmokinetics of those exposed. Most people have been assuming that only the particulate aerosols present any exposure risk. But those settle out of the atmosphere much more quickly than gas, which is absorbed immediately if inhaled in contrast to the great length of time which it takes for UO2 and U3O8 particles to dissolve in the lungs. Urine tests intended to determine exposure which measure the ratio of uranium 238 and 235 isotopes assume that only particulate aerosols and not quickly absorbed and dissolving gas have been encountered. Those urine tests have been negative for exposure in patients who have the symptoms of uranyl poisoning. Can you please help shed any light on the amount of UO3(g) produced when uranium burns in air? Thank you. Sincerely, James Salsman
- Carter, R.F. and K. Stewart (1970) "On the oxide fume formed by the combustion of plutonium and uranium" Inhaled Particles 2:819-38 speaks for itself:
- This is consistent with the very tight extrapolation of UO3(g)'s vapor pressure at the burning temperatures of uranium given in Mouradian and Baker (1963):
Temperature (K) |
Volatility of UO3(g) (mbar) |
---|---|
1250 | 10-5 |
1670 | 0.1 |
1800 | 0.34 |
2000 | 1.9 |
2200 | 8.1 |
sources: Ackermann et al. (1956) and Alexander (2005), Table 6 |
- Levinskii, Y.V. (1974) "p-versus-T Phase Diagram of the Uranium-Oxygen System" Atomic Energy 37(4):1075-6 shows that UO3 has the greatest partial pressure of all of the U-O combustion products:
- This is all consistent with the fact that at the typical burning temperatures of uranium, UO3(g) has the greatest enthalpy of formation:
Thermodynamic energies of uranium oxide gas formation at 2500 K and 1 bar | ||
---|---|---|
Compound | Gibbs free energy of formation |
Proportion as solid of particulate combustion product |
UO(g) | -592 kJ/mol | 0% |
UO2(g) | -1.14 MJ/mol | 25% |
UO3(g) | -1.57 MJ/mol | ? |
U3O8(s) | n/a - produced by condensation and decomposition of UO3(g) |
75% |
from Wanner et al. (2004) Table V.4, p. 98, and Gilchrist et al. (1979) p. ix |
- According to Rostker, B. (2000) "Depleted Uranium in the Gulf (II)" Environmental Exposure Reports Tech. Rep. No. 2000179-2 (Washington, DC: Special Assistant for Gulf War Illnesses, Department of Defense), citing Army Environmental Policy Institute (June, 1995) Health and Environmental Consequences of Depleted Uranium Use in the US Army, (Champaign, Illinois.) and U.S. Army Center for Health Promotion and Preventive Medicine (1998) Interim Summary, Total Uranium and Isotope Uranium Results, (Operation Southern Watch) CHPPM Project No. 47-EM-8111-98, uranium trioxide is produced when uranium burns.
- According to Salbu, B. et al. (2005) "Oxidation states of uranium in depleted uranium particles from Kuwait," Journal of Environmental Radioactivity, 78, 125–135, uranyl ion contamination in uranium oxides has been detected in the residue of depleted uranium munitions fires.
- There is no reliable evidence, anywhere, that uranium trioxide gas is not produced when uranium burns.
I hope that you will please review Talk:Uranium trioxide#Remaining proposed additions and add them to Uranium trioxide as well as restore mention of the gaseous combustion products on Uranium if you approve, as I have been prevented by arbitration from doing so myself. LossIsNotMore 12:07, 31 August 2006 (UTC) (formerly User:Nrcprm2026)
- Levinskii, Y.V. (1974) there is a , missing!! If you look at all other formulas in the sceme. This means that UO2.6 and UO3 are in euilibrium with a not specific gas compound or mixture. This renders this sceme useless for the UO3 gas discussion.--Stone 13:29, 31 August 2006 (UTC)
- What do you mean by "sceme"? That is not an English word. Anyway, you have no sources which support your theory that there is a missing comma, so the fact is verifiable. LossIsNotMore 23:52, 31 August 2006 (UTC)
- The sceme with measured points upto 8 mbar is useless The extrapolation to much higher temperatur and much higher vapour pressure does only make sence if the UO3 is aproofen stable particle at temperatures like 2500°C. But to reverse engenier from a sceme the stability in areagion of the plot where no data is available is wrong!--Stone 13:34, 31 August 2006 (UTC)
- Why? The prediction intervals are shown. The fact that the published data so closely fit an exponential curve is all that graph claims, not that there are actual data points in the extrapolated region. LossIsNotMore 23:52, 31 August 2006 (UTC)
- This applies only if nothing happens in between, like decomposition, or formation of a more stable form. Witch renders the plot useless, exept the claim of poison UO3 gas everywhere!--Stone 13:51, 2 September 2006 (UTC)
- Alexander should give some proof for the point that UO3 is quite stable.
- Would you please email him? He has 45 years experience publishing peer-reviewed scientific papers on uranium trioxide gas. How much experience with it do you have? LossIsNotMore 23:52, 31 August 2006 (UTC)
- There is no need for origanal research in wikipedia. This would be deleted within seconds from me or other wikipedians who apply to the established rules!--Stone 13:41, 2 September 2006 (UTC)
- The point that uranium burns and fume is created while the uranium looses weight is not a point for discussion. But where is the gas mentioned?--Stone 13:40, 31 August 2006 (UTC)
- Te definition of vapor is a substance in the gaseous state, as distinguished from the liquid or solid state. There is no way around that. LossIsNotMore 23:52, 31 August 2006 (UTC)
James, just stop asking for negative evidence "There is no reliable evidence, anywhere, that uranium trioxide gas is not produced when uranium burns": this only shows that you don't have any positive evidence for its formation, lifetime or harmful effects. Physchim62 (talk) 14:31, 31 August 2006 (UTC)
- There is plenty of positive evidence, as above, and no negative evidence anywhere. Will you agree to phone and/or email Dr. Alexander to discuss this, please? LossIsNotMore 23:52, 31 August 2006 (UTC)
1) Levinskii has no references in it, and the source of the data is not idenitified; the comma error was noted on the talk page; Olin 14:57, 31 August 2006 (UTC)
- It was published in the peer-reviewed scientific literature, and the source of the data is identified as emperical experiments. Did you read the full document? Whether there is a comma error or not, the standard for inclusion in Wikipedia is verifiability, not truth. LossIsNotMore 23:52, 31 August 2006 (UTC)
- Try it! And get baned!--Stone
(2) Carter and Stewart and Rostker do not identify the identity of the gas; if its near the vaporization point of the metal, maybe the metal is subliming; Olin 14:57, 31 August 2006 (UTC)
- No, they describe the vapor as comprising the fume component of the aerosol, which is described as oxides. You know that from several other sources, anyway. LossIsNotMore 23:52, 31 August 2006 (UTC)
- But there is no clue expect some MS measurments indicating that UO+ is the compound found in uraniumoxide vapour after ionization. Which can come from anywhere!--Stone 13:51, 2 September 2006 (UTC)
(3) the volatility graph is a gross extrapolation, and borders on original research; furthermore, an extrapolation of a physical property tells you nothing of a substance's chemical properties; Olin 14:57, 31 August 2006 (UTC)
- It is an extrapolation, but the degree-of-freedom adjusted R2 is valid, as are the 95% prediction confidence intervals shown. LossIsNotMore 23:52, 31 August 2006 (UTC)
(4) your Gibbs free energy is still miscalculated, as discussed in the UO3 talk page archives, and it borders on original research since there may be temperature dependences on the enthalpies of formation and entropies of formation; furthermore, Wanner even states that there are a lot of assumptions in the ΔH/ΔS calculation; Olin 14:57, 31 August 2006 (UTC)
- In fact, I corrected the values after you pointed out my earlier error. LossIsNotMore 23:52, 31 August 2006 (UTC)
the particulate column tells you nothing of the gas, since further reaction likely occurred; Olin 14:57, 31 August 2006 (UTC)
- Certainly, condensation (of some nonunity fraction of the gas) and decomposition occurs, which is noted in the table and confirmed by Dr. Alexander. LossIsNotMore 23:52, 31 August 2006 (UTC)
(5) the XANES spectrometry of Salbu doesn't tell you anything about the gas phase; they even state, "environmental or health impact assessments for areas affected by DU munitions should take into account the presence of respiratory UO2, U3O8 and even UO3 particles..."; (6) "There is no evidence that the tooth fairy does not exist, therefore she (he?) must exist" wouldn't convince anyone that the tooth fairy exists; (7) the UO3 page still says it decomposes to UO2, and UO2 solid/liquid is stable at high temperatures. Olin 14:57, 31 August 2006 (UTC)
- No, it doesn't say what it decomposes into, it says only that the solid decomposes, and Dr. Alexander agrees that this is the sole source of the U3O8 product observed in the particulate solids. Would you agree to speak with and/or email Dr. Alexander about this? LossIsNotMore 23:52, 31 August 2006 (UTC)
- The Salbu itself indicates a likely ness for UO3 or similar product like an uranyl salt, but it is not stated as a fact putt as a vague possibility!--Stone 13:51, 2 September 2006 (UTC)
- I strongly disagree that an explicit recommendation to consider inhaled UO3 in both the abstract and the conclusions of the paper is tantamount to reporting "a vague posibility." LossIsNotMore 03:07, 11 September 2006 (UTC)
- Olin you are so right that there is nothing to say. Except we will be accused of working for the atomic industry! So greetings from the european research facility for utalalizing uranium waste (ERFUUW spelled erfquadrupleu) to my fellow college in the american research facility for utalalizing uranium waste (ARFUUW spelled arfquadrupleu)--Stone 15:59, 31 August 2006 (UTC)
Won't anyone confirm that Dr. Alexander agrees with my interpretation of these several sources?
If you care about the truth, please do contact Dr. Alexander at the phone number or email address given above. He has told me personally that he will accept any questions on this topic, and has already been very helpful in my interactions with the NRC. Why wouldn't anyone involved in this debate want to know why someone with 45 years of experience in the subject thinks that the gas is a combustion product and is quite stable? LossIsNotMore 06:22, 2 September 2006 (UTC)
- There is no need for original research from Alexander in the Wikipedia, he can easily publish watever he has to say to you in Nature or Science or another peer reviewed paper.---Stone 13:51, 2 September 2006 (UTC)
- On the contrary, Dr. Alexander says that UO3(g) as a uranium combustion product is supported by the published sources above, and that I have been interpreting them correctly, and that those who claim that it is not have been misinterpreting the peer-reviewed published sources above. But don't take my word for it: please phone or email him as per above and ask him yourself. We are talking about the interpretation of published sources here, and not any kind of original research. Who should prevail in a dispute between anonymous Wikipedia editors who refuse to say how much experience they have with uranium trioxide gas against the word of the foremost expert in the field with over 45 years of experience in the subject? Why isn't the expert being given the benefit of the doubt?
- Are people afraid to call Dr. Alexander and speak with him, or email him, because they are afraid of being shown to have been wrong over all these many months? I suppose that is only human, but it is certainly not scientific, and it is no way to write an accurate encyclopedia.
- Badagnani, Dr. Alexander is within driving distance from you, and you have been acting as something of a neutral third party over the months. Won't you, at least, call Dr. Alexander and interview him on your own terms and let the rest of us know what he says?
- All I am asking is that you ask the foremost expert what he reads in the sources above, not that you admit it as original research, but that you take it in mind and find out the reasons for it, and compare them to the reasons that you are interpreting the sources differently than the expert, and correct the article's citation of the peer-reviewed literature accordingly. That is all I am asking here. Is that in any way unreasonable? If so, in what way? LossIsNotMore 03:04, 11 September 2006 (UTC)
- A simple peer-reviewed statement in a good journal, that says, "Uranium trioxide gas is evolved in uranium combustion. [insert cited source here]" will suffice. No phone calls necessary. No need to interpret anything. Olin 21:31, 11 September 2006 (UTC)
- I agree that would be nice to find. Why isn't Ackermann (1960)'s equilibrium equivalent to it? LossIsNotMore 04:58, 19 September 2006 (UTC)
- Ackermann is already in the article. Why not be happy with that? Furthermore, the abstract for Ackermann seems to indicate it deals a lot with UO2, not UO3. It even says, "The positive curvature [of the vapor pressure data] cannot be caused by solid monoxide or gaseous UO3 on the basis of existing thermodynamic data." [[5]]. Hard to justify referencing that. Albeit, it supports Alexander's data. But that is in the article, too. All the available data on gaseous UO3 appears to be in the article, so why are we having this discussion? If you are bent on putting your above statements with their supposedly consequent conclusions, why are you not looking at the validity of those sources? Olin 12:04, 19 September 2006 (UTC)
The red box in the sceme
Read it think obout it and belive it! There is a , missing between UO3 and G. There is no gas compound specified in the sceme! Sorry if you realy think that everything published in correct spelling!--Stone 13:39, 2 September 2006 (UTC)
- I don't mean to be rude, but I've spent weeks trying to figure out what you are complaining about. Would you please replace "sceme" with an English word which means what you are trying to say? "Sceme" is not an English word. LossIsNotMore 03:05, 11 September 2006 (UTC)
The sceme is wrong man the is missing man the is missing!--Stone 06:46, 11 September 2006 (UTC)
- ?????????? Badagnani 07:18, 11 September 2006 (UTC)
- Also, um, the supposed UO3G is on the low temperature end of the scale, not anywhere near the combustion temperature. Russian journals are notoriously bad. And, um, they really need to explain where they got the data from. There are no references in that article. How can you justify it as a source, when there is no sources or explanation of the experimental data in the paper? The reliable sources guideline for Wikipedia clearly excludes this as a source. Olin 12:34, 15 September 2006 (UTC)
Uranium (from WikiProject Chem)
(Copied from WikiProject Chemistry)
There is a long-running dispute concerning whether uranium trioxide gas is a combustion product of uranium. I have found an expert, Dr. Carl Alexander at Battelle, with 45 years of experience in the subject, who claims that the research literature I have cited indicates that the gas is a combustion product. A handful of editors stridently opposing me have for several months claimed that the gas is not a combustion product, without any sources supporting that point of view. I ask that a neutral third party WikiProject participant please phone or email Dr. Alexander, at the number and/or address given at Talk:Uranium trioxide#Discussion from Wikipedia talk:WikiProject Chemistry, and ask him for the reasons he feels that the sources cited there support his and my view that uranium trioxide gas is a combustion product of uranium, and share his responses with all on Talk:Uranium trioxide. Thanks in advance. LossIsNotMore 03:22, 11 September 2006 (UTC)
- A simple peer-reviewed statement in a good journal, that says, "Uranium trioxide gas is evolved in uranium combustion. [insert cited source here]" will suffice. No phone calls necessary.Olin 21:29, 11 September 2006 (UTC)
- There is a U.S. Army publication that states just that, which has been discussed at some length here. No valid reason has been given for dismissing the very clear statement in that source, which says just what you state. Badagnani 22:01, 11 September 2006 (UTC)
- Is the U.S. Army publication peer-reviewed? What data do they have to support that it is UO3 gas that a scientist would understand? If it's being used as a secondary source, where's the evidence in that data? There would be much more credibility if it's in an ACS or RSC journal, preferably in the modern age. (If is Jette et al., I can't tell from above, it doesn't say that, btw). Besides, my other point is, a phone call from Dr. Alexander does not a reference make. Furthermore, it's clearly James trying to push a POV in an article by highlighting information that is largely unimportant--the bigger issue here. Olin 15:34, 12 September 2006 (UTC)
- I don't know if it was peer reviewed but since it is a military publication perhaps not. I'm not certain that peer review is a standard for Wikipedia, given that the information is from a reputable source and is verifiable. Whatever the case, you must have read that source because we've discussed it many times, but it doesn't specify what form (i.e. gas, solid, particulate, etc.) the uranium trioxide is in upon combustion. What form would you guess it is in in such a situation (pyrophoric explosion of tank-penetrating shell)? We're dancing around the issue, and it does need to be addressed. It seems as if the two camps are *hoping* either that UO3 is, or isn't formed during such combustion. Both can't be right and the sources do state that such a material is formed. Now it is up to us to ascertain the veracity of this and add it to the article. This discussion shows that no one can say we didn't do our work thoroughly here! Perhaps Dr. Alexander's next experiment should be to blow up a tank with a DU shell and collect the combustion products, for his next peer reviewed paper--God knows, it's an issue of significance right now considering the material's widespread use. But, then again, the U.S. military seems to have already tried this, as their publication is quite clear that UO3 (in whatever form) is a product of such combustion. Badagnani 17:58, 12 September 2006 (UTC)
- Is the U.S. Army publication peer-reviewed? What data do they have to support that it is UO3 gas that a scientist would understand? If it's being used as a secondary source, where's the evidence in that data? There would be much more credibility if it's in an ACS or RSC journal, preferably in the modern age. (If is Jette et al., I can't tell from above, it doesn't say that, btw). Besides, my other point is, a phone call from Dr. Alexander does not a reference make. Furthermore, it's clearly James trying to push a POV in an article by highlighting information that is largely unimportant--the bigger issue here. Olin 15:34, 12 September 2006 (UTC)
- There is a U.S. Army publication that states just that, which has been discussed at some length here. No valid reason has been given for dismissing the very clear statement in that source, which says just what you state. Badagnani 22:01, 11 September 2006 (UTC)
- A simple peer-reviewed statement in a good journal, that says, "Uranium trioxide gas is evolved in uranium combustion. [insert cited source here]" will suffice. No phone calls necessary.Olin 21:29, 11 September 2006 (UTC)
- No. It is not up to us to define the veracity of this. It is up to the scientific community to publish it in a peer-reviewed journal, and then it can be properly sourced. It has nothing to do with us. That's one of the major points. (See Wikipedia:Verifiability for more about peer review. For academic subjects (this must qualify), peer review is "preferable," and for "outlandish claims" (words on the page, not mine) you need "stronger sources." I'm assuming by "outlandish" that would include "contraversial.") No phone call or e-mail is peer-reviewed. If one tried to cite this in a scientific article, you would be shot down immediately. In fact, if you put a non-peer reviewed source in a paper for college, you should be marked down. It is the major reason why most colleges won't accept wikipedia articles as sources in papers.
- The other major point is that the article shouldn't overemphasize something because someone wants it for political gain.
- (The quote on this page says something about μm. I highly doubt an 'isolated' UO3 molecule is that big, considering most molecules are in the pm range of size.)
- It is that lack of critical analysis, and moreso the forcing of analysis to fit an agenda, that disturbs me most about this discussion.Olin 19:51, 12 September 2006 (UTC)
- Since you have such great expertise in the matter, why not simply state the reaction products (including various gases which are doubtless formed) that you believe to be formed during the battlefield combustion of DU munitions? Not to throw this in your face, but the willful failure to address the issue does, unfortunately, tend to show a similar political agenda. This question, each time it is asked, doesn't ever seem to be answered, but is instead countered by claims that bringing up the very relevant subject is "outlandish," or that the only person interested in pursuing the issue has been banned, etc. To return to the original subject, it doesn't matter the size of the particles produced, if they're produced, they're produced and the Army source says so. I don't think the Army hires unqualified personnel to prepare such reports and thus the source is verifiable. Do you impugn the qualifications of the writers of that publication and if so what is your justification for doing so? Badagnani 23:23, 12 September 2006 (UTC)
- No, no, no, no, no. My opinion is not relevant. Reread the above. It's about providing reliable sources in a page, not anyone's opinion or constructed argument (which is original research). (The word "outlandish" is a word on the Wikipedia:Verifiability page, not my word, btw, I was not saying that the idea is outlandish. I don't want to be accused of a personal attack for that term.) THe concept that is set-out over and over again is that gaseous UO3 is produced upon combustion, so solid particles do not count.
- You are never going to get acceptance for putting a source here from the chemistry community (or, I suspect, the scientific community), unless you provide a source from a chemistry journal, and since this is controversial, likely an American Chemical Society journal or Royal Chemical Society journal. This is not an article about weaponry. That you use the word depleted uranium instead of just uranium shows your bias. It is not up to me to put here what I think is going on--the burden of proof is on the editor which chooses to include such information. The other editors have the right to challenge the quality of the data, and the interpretation of the data (which should not have to be interpreted). (That is why the vapor pressure stands in the article--it is concrete data in a decent peer-reviewed journal.)
- I choose not to search for the information, because it is no real consequence to a casually browsing chemist or a nonexpert on the topic. The gas properties of UO3 is a minor topic on the physical and chemical properties of UO3. I seriously doubt there are many other pages about metal oxides which focus on their gas-phase properties, although I do not have statistics.
- It's not a politics thing, it's an educated chemist thing.Olin 12:27, 13 September 2006 (UTC)
- Is the opinion of the world's foremost expert on the subject, with over 45 years of experience on it, not exceptional evidence? He claims that the cited sources show that the gas is a combustion product. Why don't you pick up the phone or send an email and find out why? LossIsNotMore 04:56, 19 September 2006 (UTC)
If you can get his phone call peer-reviewed, we can gladly add it to the the article. Read the policy on reliable sources above. Olin 12:00, 19 September 2006 (UTC)
Reasons why Dr. Alexander's phone call is no good as evidence:
- WP:RS: "A self-published source is a published source that has not been subject to any form of independent fact-checking, or where no one stands between the writer and the act of publication. [Usually, these are not acceptable. However,] Exceptions to this may be when a well-known, professional researcher writing within his field of expertise, or a well-known professional journalist, has produced self-published material. In some cases, these may be acceptable as sources, so long as their work has been previously published by credible, third-party publications, and they are writing under their own names, and not a pseudonym. In general it is preferable to wait until other sources have had time to review or comment on self-published sources." (Notably, a phone call isn't even self-published.)
Why a synthesis of articles does not give "Gaseous UO3 as a combustion product":
- WP:OR: "Editors often make the mistake of thinking that if A is published by a reliable source, and B is published by a reliable source, then A and B can be joined together in an article in order to advance position C. However, this would be an example of a new synthesis of published material serving to advance a position, and as such it would constitute original research. 'A and B, therefore C' is acceptable only if a reliable source has published this argument in relation to the topic of the article."
Olin 22:21, 19 September 2006 (UTC)
- Don't forget, the Army source states that uranium trioxide is formed during the battlefield combustion of DU munitions. It doesn't specifically state that gas is formed. So, the question is: is fine particulate of uranium trioxide formed during such combustion? The source does clearly state that uranium trioxide is formed. The next following question would be, does such fine particulate count as a "gas" following the normal definition of the term "gas"? If not, why not just call it "fine particulate" or whatever terminology is most accurate? Let's stop dancing around the question and figure out why that Army source clearly states that uranium trioxide is formed. A user above has stated that this is not really of interest. Perhaps to someone interested primarily in theoretical chemistry and not in real-life uses, it's not of great interest. But seeing the widespread use of DU in this context, the products of such combustion (particularly to people living or working in regions where it's used) is of great interest to many people around the world. Badagnani 22:27, 19 September 2006 (UTC)
- (Well, since you don't want to talk about quality and validity of sources or synthesizing data, why not?) See colloid (or a general chemistry book that contains a section on colloids), which is distinctly different than a gas even in the nonscientific, likely non-peer reviewed source. Olin 15:52, 20 September 2006 (UTC)