Talk:Uranium trioxide/Archive 1

message: As mentioned on Wikipedia talk:Requests for mediation/Depleted uranium and related articles, there are now scans of new source articles in:
  http://www.bovik.org/du/scans/
--James S. 05:42, 23 February 2006 (UTC)
thread_title:  Source scans 

message: I moved the discussion of UO3 gas into comment temporarily until I can look into the literature.  Anyway, gaseous UO3 seems to be a minor aspect of the basic chemistry of the material uranium trioxide, which is what readers will be seeking in this article.  The next order of business might be to describe the solid state coordination environment of UO3 and its simple hydrates, as summarized in "Structural Inorganic Chem." --Smokefoot 18:10, 24 February 2006 (UTC)
thread_title: UO3 solid and gas

message: Hi Nrcprm2026 it looks like you are editing UO3 article e.g. by inserting "UO3 bond angles are about 90 and 180 degrees, with bond lengths between 1.2 and 2.2 Angstroms; the narrower uranium ion is in the central position."
The phrasing is unusually non-chemical, and more specifically the bond angles and distances also seem unexpected.  I was wondering if this is a joke or something?I was going to edit this silly phrase but I get the feeling that there's a joke going on here. --Smokefoot 00:44, 25 February 2006 (UTC)
replies: text: The joke is hereWikipedia:Requests for mediation/Depleted uranium and related articles/UO3 vapor and the punch line is hereWikipedia:Requests for mediation/Depleted uranium and related articles. --DV8 2XL 01:07, 25 February 2006 (UTC)
thread_title: UO3 molecular structure

message: Why does Smokefoot claim DV8 2XL's edit? --James S. 05:16, 25 February 2006 (UTC)
replies: text: Are you the same person as DV8 2XL?  And, what do you think the variance of the bond lengths are at STP? --James S. 05:49, 25 February 2006 (UTC)
replies: text:  No I am smokefoot and inorganicker, I have observed DV8 2XL making edits on UO3 that looked ok to me.  At STP, UO3 is a rock, i.e. a polymeric coordination solid with a high coordination number.  As others know better than me, UO3 is a particularly complex material since apparently several polymorphs exist.  I was hoping to describe the structure in the UO3 article but this gas-phase stuff keeps appearing, and I am not familiar with the recent chemical physics of that molecule, if it even exits. Also it appears that UO3 is a politically lively topic, which really  complicates any discussion of the geeky inorganic chem, so I am going to let you folks battle this one out. --Smokefoot 06:03, 25 February 2006 (UTC)

text: In fact I insist that you do James; then I will expect your apology here and on smokefoots, mine and your talk pages --DV8 2XL 15:01, 25 February 2006 (UTC)
replies: text:  Why do you suppose Smokefoot described an edit that you made? --James S. 18:11, 25 February 2006 (UTC)

text: A simple check on "User contributions" would have permitted an editor with good faith to assure themselves that these two editors are different people. I have had a CheckUser request run, and it shows that they edit from different countries. I simply cannot tolerate the harrassment of editors who are prima facie not involved in the dispute under mediation: given the choice between protecting the articles and taking the dispute back to the Arbitration Committee, I have chosen the latter. Physchim62 (talk) 14:44, 26 February 2006 (UTC)
replies: text:  If you think my suspicions were unfounded, then why did you run a checkuser to begin with? There is no question that Smokefoot described DV8 2XL's edit as his own, is there? --James S. 17:18, 26 February 2006 (UTC)
thread_title:  DV8 2XL and Smokefoot are two different people 

message: With a melting point of 500°C there is no gas at 400°C during the synthesis!--Stone 16:50, 14 March 2006 (UTC)
replies: text: The solid decomposes before it melts.  If I knew the specific heat capacity, then we could learn the temperature at which the gas decomposes. It's above the burning temperature. --James S. 11:39, 17 March 2006 (UTC)
thread_title:  Melting Point

message: Normal methode for purification is chemical transport reaction. Ackermann writes it in his paper that he uses it do purify the U3O8 and to get crystals. There is tonns of literature on chemical transport reactions. ( Holleman Wieberg, Lehrbuch der Anorganischen Chemie 1985, for the Mond process)--Stone 16:50, 14 March 2006 (UTC)
replies: text: Please see below. --James S. 11:39, 17 March 2006 (UTC)
thread_title:  Mond process 

message: I was looking at WebElements UO3 page.  Under melting point, it says decomposes to to U3O8 - does anyone know what temperature this happens at?
Following the link to the U3O8 page, I find the m.p. is given as 1150 °C; 1300 °C decomposes to UO2.  And UO2's m.p. is given as 2827 °C.  It would be nice to have this information stated simply in a section or in the infobox.  I'm scared to touch this article, though, for all the heated debate I've seen on the talk page and elsewhere.
If this info is accurate, there should be a sequence of events like this:
UO3(s) → (at ?°C) → U3O8(s) → (at 1150°C) → U3O8(l) → (at 1300°C) → UO2(s) → (at 2827 °C) → UO2(l)
I'm finding this article a bit confusing to read.  Can the basic chemistry (that all textbooks agree on!) be near the top of the article, leaving the row about UO3 gas for the bottom of the page.  I know I'm only a student and I don't have seven PhD's like most of you who contribute to this article, but I'm sure many, if not most, people who look for uranium trioxide on Wikipedia aren't experts and would prefer the simple information first.
:Surprisingly enough, the temperature that you want is not known with certainty. The best I value I can see for the moment is somewhere between 150 °C and 600 °C, depending on your belief in different sources. U3O8 itself is reported to start losing oxygen at 800 °C (Gmelin): NIST data gives an equilibrium temperature of 182 °C, although other direct experimental studies suggest that solid UO3 (probably with oxygen defects) is at least metastable at higher temperatures. Physchim62 (talk) 17:09, 15 March 2006 (UTC)
thread_title:  Decomposition of UO<sub>3</sub> to U<sub>3</sub>O<sub>8</sub> 

message: I found the following sections to be unsupported so I removed them:
:Uranium trioxide molecules are a postulated intermediate in the chemical transport reaction forming U3O8 crystals. This reaction is closely related to other chemical transport reactions, for example the Mond process for purifying nickel
:Solid UO3 decomposes at temperatures greater than 150 °C releasing O2 to afford high surface area UO2
--James S. 23:28, 14 March 2006 (UTC)
replies: text: What do you mean they are unsupported? James they are supported by your very own references. Maybe you should take the time to read them yourself. --DV8 2XL 01:05, 15 March 2006 (UTC)
replies: text: "postulated" is too weak for the spectrographic detection cited.  "Closely related" seems too strong -- the only relation seems to be metal reactions in a gaseous solution.  (So, would all aqueous reactions be "closely" related because they involve liquid water -- water is more specific than metals in general?)  The decomposition temperature of UO3(s) has been claimed here, over the past month, at widely divergent temperatures, and I'd just like to get a source reference for that temperature, please. --James S. 16:29, 15 March 2006 (UTC)
replies: text: You are not talking sense. Many editors from the Chem project have looked at your citations and found you in error. You are going to loose this fight for the simple reason that you are wrong. Why you continue to assert these untruths in the face of so much evidence that you are misinterpreting your own sources is beyond me. --DV8 2XL 17:00, 15 March 2006 (UTC)
replies: text: Please try to remain civil and refrain from making personal attacks.  I have added a link to the "keep a cool head"  page to the top of this talk page which may help. --James S. 17:03, 15 March 2006 (UTC)
thread_title:  Sections removed as unsupported 

message: Uranium is oxidized to Uranium trioxide and than sublimated to form Uranium trioxide gaseous.  AAA kJ/mol
Uranium is evaporated and than oxidised in gas phase to Uranium trioxide gaseous.  BBB kJ/mol
Uranium and oxygen form a plasma and while cooling oxidised in gas phase to Uranium trioxide gaseous.  CCC kJ/mol
AAA=BBB=CCC
It does not matter which way to get to the Uranium trioxide gaseous all energies are the same. 
--Stone 14:08, 16 March 2006 (UTC)
replies: text: AAA is not a number because solid decomposition occurs before sublimation. --James S. 12:00, 17 March 2006 (UTC)
thread_title: Oxidation

message: The reaction from Uranium trioxide gaseous to Uranium trioxide solid is a simple sublimation reaction. DDD kJ/mol
The way this sublimation is going makes no difference for the energy. Energy for sublimation is DDD and for condensation is –DDD. 
If the energy for sublimation is large the energy for condensation is also large too. The low vapour pressure at 2300K of  0.34 Pa indicates clearly that the energy for sublimation is high. 
With this high energy the energy for condensation is also high.
Statement: The energy for sublimation is high. (or not?)
This lead to fast condensation to the solid Uranium trioxide. 
If there is a compound with a low vapour pressure or high energy for sublimation and forms a gas as a predominant species over a broad range of temperature and pressure this would harm hurt or kill the Born Haber Cycle and  a perpetuum mobile would be in accessible in an easy way. 
There is no chance that with 0.34 Pa at 2300K (or is this number also under discussion?) that there is more Uranium trioxide is in gas phase at lower temperature. Condensation reaction takes place at any particle in the atmosphere till equilibrium is reached. This equilibrium has to be on the side of Uranium trioxide not the gas phase.
--Stone 14:08, 16 March 2006 (UTC)
replies: text: What are the mean distances a uranium trioxide molecule in air would traverse, linear and total? --James S. 12:03, 17 March 2006 (UTC)
replies: text: Within the dense cloude of an Uranium fire mm not more than cm.--217.185.17.145 11:04, 19 March 2006 (UTC)
replies: text: Source?  Show your work?  --James S. 19:27, 19 March 2006 (UTC)
replies: text: You have not showed any proof for your gasous UO3 will be in atmosphere for weeks either! So what! There are only three MS articles showing evidence for UO3 and all other show nothing, even Gmelin does not give anything about it.--Stone 07:17, 20 March 2006 (UTC)
replies: text:  Please review the diffusion and settling rates of particles on the scale of five angstroms with the CRC Handbook's particle dispersoid chart.  Water condenses, too, but still in many places the humidity remains above zero.  Gmelin specifically states that the "taking up of oxygen by U3O8" is "not infrequently ignored," citing Ackermann (1960.)  Your edits show that you have either not read or that you have failed to understand the texts to which you refer.  --James S. 21:15, 20 March 2006 (UTC)

text: Please try to keep from confusing the pressures of UO3(g) sublimation in near-vacuum for late-1950s spectrography used to derive thermodynamic formation data with UO3(g) formation from ionic plasma after combustion. 
The reaction is somewhat different but the reaction which is important is the reaction back to the solid phase which is the same and hase the same energy. It is not important where you come from! --Stone 11:53, 19 March 2006 (UTC)
thread_title:  Uranium trioxide gaseous 

message: UO3 vapor; Total inhalation exposure; Teratogenicity; Neurotoxicity; Carcinogenicity; and other questions from "Can the value of a human poison be known without knowledge of its long-term effects?" to "Does the oxygen gradient in a fire modify the effective surface area of burning particles by a scalar value?" (history.) --James S. 08:54, 17 March 2006 (UTC)
thread_title:  Discussion from mediation 

message: === Born Harber cycle ===
Please leave these calculations alone, if you want to comment please do so in the sub section marked comments. I am making a point of doing the calculations in plain sight.
For the conversion of uranium metal to the monoatomic gas at STP, DeltaH = 533.0 +- 8.0 KJ mol-1
If we assume the reaction 2U + 3O2 to make 2UO3 then we can assume that the oxygen atoms (arrnaged in molecules are already in the gas phase. So no heat is required to form the oxygen gas.
Using Hess's Law, as the Delta H of formation of UO3 gas (from metallic U) is listed at -799.2 KJ mol-1, we can assume that the energy for the conversion of the monoatomic gas to the UO3 gas is 1332.2 KJ mol-1. This has allowed us to get to the point where we can draw a simple Born Haber cycle. This is rather mundane.
The next step is more interesting, assume that a uranium fire occurs in air (20% O2 and 80% N2). For the purposes of the calculation assume that the uranium oxide product is in the form of a gas.
2U + 3 O2 + 12 N2 --> 2 UO3 + 12 N2
We can expect that the reaction will generate 799.2 KJ mol-1
If we assume that no heat is transfered (adiabatic) system the it is possible to eastimate the flame temperture. I hope to goodness that this does not start a flame war, dire pun
The molar heat capacity of UO3 gas listed in my fav. source is 64.5 (plus minus 2) J K-1 mol-1
 states that the molar heat capacity of nitrogen is 20.8 J K-1 mol-1
So the heat capacity of 2 UO3 + 12 N2 will be (2 x 64.5) + (12 x 20.8) J K-1 mol-1
Which is 189.3 J K-1 mol-1 for each mole of uranium which burns. Call this Cx
Each mole of uranium which burns to make the gas, will give out 799.2 KJ (Delta H)
T = 298 K + (Delta H/Cx) = 298 + 4222 K = 4520 K
This is going to be very hot, and could cause uranium oxide gas to form for a moment. As the mixture is cooled by mixing with more air, the uranium oxide will then condense. The calculation which I have done is for a rare case of uranium being vapourised and then oxidised, this would happen in reactive spluttering where in an argon/oxygen gas at low preasure uranium atoms are spalled off of a surface by plasma discharge. So I think that it is reasonable to assume that uranium trioxide gas can be formed (for a moment) by burning uranium under a set of idealised conditions, but I expect that it will rapidly condense onto a surface.
Anyone who wants to is welcome to check my maths:) Cadmium
==== Comments on the Born Harber cycle ====
Flame temperature data. --James S. 20:14, 17 March 2006 (UTC)
replies: text: 2570K is the highest combustion temp that I can see in this reference. Of what pertenance to Cd's calculations can this be? At best it would seem to imply that any UO3(g) that's formed from compustion in open air wouldn't make it past the flame boundary before condensing, if that. --DV8 2XL 21:55, 20 March 2006 (UTC)
replies: text: The point is that it's above the 2000 K point at which U3O8 continues to burn. --James S. 23:23, 20 March 2006 (UTC)
replies: text: Not at 1 atm. - it decomposes at 1573.15 kelvin - to UO2 which is a solid to 3100.15 kelvin. Numbers aren't there James. --DV8 2XL 00:28, 21 March 2006 (UTC)
replies: text: If that were the case, then UO2(s) would comprise more than 25% of the particulate combustion product, and U3O8 less than 75%.  What source are you using? --James S. 00:37, 21 March 2006 (UTC)
replies: text: A lot of the final product will come from the cooler parts of the combustion enveolpe - this is more due to the physics of the flames geometry than the chemistry. I got the numbers from my Rubber Bible. --DV8 2XL 02:13, 21 March 2006 (UTC)
replies: text: So, what does your rubber bible say that U3O8 decomposes into, and what source does it give for that temperature? --James S. 16:41, 21 March 2006 (UTC)
replies: text: The decomposition product is UO2: the temperature is consitent with the NIST thermodynamic data for the two species (even if there are far too many sig. figs.!). Physchim62 (talk) 16:31, 22 March 2006 (UTC)

text: Kinetic and thermodynamic products at different reaction conditions can differ a lot! Thermodynamic reactions can be favoured but because of the reaction partners or a sharp drop in temperature where the activation energy for the exothermic reaction is no longer present they can be kinetically hindered. So U3O8 or UO3 what are they kinetical or thermodynamic products and at what temperatures under what conditions. Without all the data, asuming  which of them is in the burningproducts in gas phase of DU, is speculative or even missleading! The only thing which is shure is that nobody ever detected UO3 over burning DU (Yes Ackermann showed it but only as best presumption he could make, because he had no MS of his gas phase). Only as endproduct of the burning as solide. So state this and leave the rest as speculation, what it realy is!--Stone 09:59, 21 March 2006 (UTC)

text: Which is why this whole line of inquiry is perilously close to violating WP:NOR, Like Stone is saying; withhout hard clear references we are moving into specualtion. --DV8 2XL 15:15, 21 March 2006 (UTC)
replies: text: In fact, Salbu et al. (2005) did detect UO3 in combustion residues.  This is not speculation or original research, the fact of UO3(g) is supported by an abundance of sources from the scholarly and peer-reviewed scientific literature.  The irony of being asked for "hard clear references" is palpable. It is clear from the edits to this page that those wishing to downplay or suppress the reality of uranyl compounds as aerial combustion products of uranium have no better familiarity with the  scientific literature than some of them do with the English language. It is not my responsibility to prove verification of sources I have already verified, and I doubt it is my responsibility to try to understand the tortured ambigious spellings and grammar as have recently become so plentiful here.  However, that doesn't mean that I won't continue to try, because I think this is important, and the practice is good preparation for real-time debate, and it's like shooting fish in a barrel. --James S. 16:41, 21 March 2006 (UTC)
replies: text: In fact, Salbu et al. (2005) did detect UO3. This is fully right and this fact was never disputed! But this is not a gas but a solid particles as you can read in the abstract! So this is no proof for the gas, give proof for gas at normal conditions!--Stone 16:58, 21 March 2006 (UTC)
replies: text: Actually, this is disputed: Salbu's results are equally, if not more, consitent with U3O8 as the solid product formed from the munitions dump fire. Physchim62 (talk) 16:31, 22 March 2006 (UTC)

text: Again, Wilson (1961) p. 213. The statistical dynamics involve the number of gas molecules unable to glom onto others before reaching open air; this number is some fraction, not zero. --James S. 17:58, 21 March 2006 (UTC)
replies: text: The pressure of Iron over a pice of iron is not zero eiter but nobody would say it is a amount which has any significance. Even above ice there are a lot of molecules of water present. If going 200°C below freezing point like on titan you find no water in the atmosphere at all. mare than 500°C below the point you can detect it you will find molecules in gas phase but if you inhale all the air from Uranium trioxide for years you would not get more than drinking a glas of mineral water. --Stone 08:15, 22 March 2006 (UTC)
replies: text: You said something about raman spectroscopy. This is not a MS methode at all it si a spectroscopy methode determine the fibrations and flexing in a molecule, but it is not suitable for determining the molecular mass of molecule. But if you have a good raman spectra of a UO3 at standart conditions this would also qualify as source for UO3 gas. --Stone 08:15, 22 March 2006 (UTC)
replies: text:  Please stop quoting willson, because if you dont stop I have to give back the compliment you made: Do you ever read what you are quating?
Willson has done no research on UO3 he only quotes the ackeman paper nothing more. --Stone 08:53, 23 March 2006 (UTC)

text: You mean, other than actually burning uranium and measuring the gas condensates by observation of crystals? --James S. 10:17, 23 March 2006 (UTC)
replies: text: The page 213 you always revere to is basically a quote. And the rest of the paper deals with the real burning products of uranium not mentioning UO3 as significally imortant any more.--Stone 10:42, 23 March 2006 (UTC)
replies: text: And Salbu's similar description of UO3-rich condensates? --James S. 11:25, 23 March 2006 (UTC)
replies: text: As stated in some older publications U3O8 was contributed as UO2+2(UO3) so U03 rich says nothing. U03 solide is not ever questioned the gas is the problem! --Stone 11:35, 23 March 2006 (UTC)
replies: text: Salbu's description were of particles in which the oxidation state of uranium was +5.5±0.5: this is more consistent with U3O8 (oxidation state +5.33) than UO3 (oxidation state +6). This also fits with the normal description of U3O8 as the product of burning uranium in the presence of excess oxygen. Salbu also looked for uranyl carbonate, which would be formed by weathering of U3O8: they were unable to verify or to rule out its presence. Physchim62 (talk) 12:55, 23 March 2006 (UTC)
thread_title:  Copied from ArbCom page by DV8 2XL - of more value here  

message: Please leave these calculations alone, if you want to comment please do so in the sub section marked comments. I am making a point of doing the calculations in plain sight.
For the conversion of uranium metal to the monoatomic gas at STP, DeltaH = 533.0 +- 8.0 KJ mol-1
If we assume the reaction 2U + 3O2 to make 2UO3 then we can assume that the oxygen atoms (arrnaged in molecules are already in the gas phase. So no heat is required to form the oxygen gas.
Using Hess's Law, as the Delta H of formation of UO3 gas (from metallic U) is listed at -799.2 KJ mol-1, we can assume that the energy for the conversion of the monoatomic gas to the UO3 gas is 1332.2 KJ mol-1. This has allowed us to get to the point where we can draw a simple Born Haber cycle. This is rather mundane.
The next step is more interesting, assume that a uranium fire occurs in air (20% O2 and 80% N2). For the purposes of the calculation assume that the uranium oxide product is in the form of a gas.
2U + 3 O2 + 12 N2 --> 2 UO3 + 12 N2
We can expect that the reaction will generate 799.2 KJ mol-1
If we assume that no heat is transfered (adiabatic) system the it is possible to eastimate the flame temperture. I hope to goodness that this does not start a flame war, dire pun
The molar heat capacity of UO3 gas listed in my fav. source is 64.5 (plus minus 2) J K-1 mol-1
 states that the molar heat capacity of nitrogen is 20.8 J K-1 mol-1
So the heat capacity of 2 UO3 + 12 N2 will be (2 x 64.5) + (12 x 20.8) J K-1 mol-1
Which is 189.3 J K-1 mol-1 for each mole of uranium which burns. Call this Cx
Each mole of uranium which burns to make the gas, will give out 799.2 KJ (Delta H)
T = 298 K + (Delta H/Cx) = 298 + 4222 K = 4520 K
This is going to be very hot, and could cause uranium oxide gas to form for a moment. As the mixture is cooled by mixing with more air, the uranium oxide will then condense. The calculation which I have done is for a rare case of uranium being vapourised and then oxidised, this would happen in reactive spluttering where in an argon/oxygen gas at low preasure uranium atoms are spalled off of a surface by plasma discharge. So I think that it is reasonable to assume that uranium trioxide gas can be formed (for a moment) by burning uranium under a set of idealised conditions, but I expect that it will rapidly condense onto a surface.
Anyone who wants to is welcome to check my maths:) Cadmium
==== Comments on the Born Harber cycle ====
Flame temperature data. --James S. 20:14, 17 March 2006 (UTC)
replies: text: 2570K is the highest combustion temp that I can see in this reference. Of what pertenance to Cd's calculations can this be? At best it would seem to imply that any UO3(g) that's formed from compustion in open air wouldn't make it past the flame boundary before condensing, if that. --DV8 2XL 21:55, 20 March 2006 (UTC)
replies: text: The point is that it's above the 2000 K point at which U3O8 continues to burn. --James S. 23:23, 20 March 2006 (UTC)
replies: text: Not at 1 atm. - it decomposes at 1573.15 kelvin - to UO2 which is a solid to 3100.15 kelvin. Numbers aren't there James. --DV8 2XL 00:28, 21 March 2006 (UTC)
replies: text: If that were the case, then UO2(s) would comprise more than 25% of the particulate combustion product, and U3O8 less than 75%.  What source are you using? --James S. 00:37, 21 March 2006 (UTC)
replies: text: A lot of the final product will come from the cooler parts of the combustion enveolpe - this is more due to the physics of the flames geometry than the chemistry. I got the numbers from my Rubber Bible. --DV8 2XL 02:13, 21 March 2006 (UTC)
replies: text: So, what does your rubber bible say that U3O8 decomposes into, and what source does it give for that temperature? --James S. 16:41, 21 March 2006 (UTC)
replies: text: The decomposition product is UO2: the temperature is consitent with the NIST thermodynamic data for the two species (even if there are far too many sig. figs.!). Physchim62 (talk) 16:31, 22 March 2006 (UTC)

text: Kinetic and thermodynamic products at different reaction conditions can differ a lot! Thermodynamic reactions can be favoured but because of the reaction partners or a sharp drop in temperature where the activation energy for the exothermic reaction is no longer present they can be kinetically hindered. So U3O8 or UO3 what are they kinetical or thermodynamic products and at what temperatures under what conditions. Without all the data, asuming  which of them is in the burningproducts in gas phase of DU, is speculative or even missleading! The only thing which is shure is that nobody ever detected UO3 over burning DU (Yes Ackermann showed it but only as best presumption he could make, because he had no MS of his gas phase). Only as endproduct of the burning as solide. So state this and leave the rest as speculation, what it realy is!--Stone 09:59, 21 March 2006 (UTC)

text: Which is why this whole line of inquiry is perilously close to violating WP:NOR, Like Stone is saying; withhout hard clear references we are moving into specualtion. --DV8 2XL 15:15, 21 March 2006 (UTC)
replies: text: In fact, Salbu et al. (2005) did detect UO3 in combustion residues.  This is not speculation or original research, the fact of UO3(g) is supported by an abundance of sources from the scholarly and peer-reviewed scientific literature.  The irony of being asked for "hard clear references" is palpable. It is clear from the edits to this page that those wishing to downplay or suppress the reality of uranyl compounds as aerial combustion products of uranium have no better familiarity with the  scientific literature than some of them do with the English language. It is not my responsibility to prove verification of sources I have already verified, and I doubt it is my responsibility to try to understand the tortured ambigious spellings and grammar as have recently become so plentiful here.  However, that doesn't mean that I won't continue to try, because I think this is important, and the practice is good preparation for real-time debate, and it's like shooting fish in a barrel. --James S. 16:41, 21 March 2006 (UTC)
replies: text: In fact, Salbu et al. (2005) did detect UO3. This is fully right and this fact was never disputed! But this is not a gas but a solid particles as you can read in the abstract! So this is no proof for the gas, give proof for gas at normal conditions!--Stone 16:58, 21 March 2006 (UTC)
replies: text: Actually, this is disputed: Salbu's results are equally, if not more, consitent with U3O8 as the solid product formed from the munitions dump fire. Physchim62 (talk) 16:31, 22 March 2006 (UTC)

text: Again, Wilson (1961) p. 213. The statistical dynamics involve the number of gas molecules unable to glom onto others before reaching open air; this number is some fraction, not zero. --James S. 17:58, 21 March 2006 (UTC)
replies: text: The pressure of Iron over a pice of iron is not zero eiter but nobody would say it is a amount which has any significance. Even above ice there are a lot of molecules of water present. If going 200°C below freezing point like on titan you find no water in the atmosphere at all. mare than 500°C below the point you can detect it you will find molecules in gas phase but if you inhale all the air from Uranium trioxide for years you would not get more than drinking a glas of mineral water. --Stone 08:15, 22 March 2006 (UTC)
replies: text: You said something about raman spectroscopy. This is not a MS methode at all it si a spectroscopy methode determine the fibrations and flexing in a molecule, but it is not suitable for determining the molecular mass of molecule. But if you have a good raman spectra of a UO3 at standart conditions this would also qualify as source for UO3 gas. --Stone 08:15, 22 March 2006 (UTC)
replies: text:  Please stop quoting willson, because if you dont stop I have to give back the compliment you made: Do you ever read what you are quating?
Willson has done no research on UO3 he only quotes the ackeman paper nothing more. --Stone 08:53, 23 March 2006 (UTC)

text: You mean, other than actually burning uranium and measuring the gas condensates by observation of crystals? --James S. 10:17, 23 March 2006 (UTC)
replies: text: The page 213 you always revere to is basically a quote. And the rest of the paper deals with the real burning products of uranium not mentioning UO3 as significally imortant any more.--Stone 10:42, 23 March 2006 (UTC)
replies: text: And Salbu's similar description of UO3-rich condensates? --James S. 11:25, 23 March 2006 (UTC)
replies: text: As stated in some older publications U3O8 was contributed as UO2+2(UO3) so U03 rich says nothing. U03 solide is not ever questioned the gas is the problem! --Stone 11:35, 23 March 2006 (UTC)
replies: text: Salbu's description were of particles in which the oxidation state of uranium was +5.5±0.5: this is more consistent with U3O8 (oxidation state +5.33) than UO3 (oxidation state +6). This also fits with the normal description of U3O8 as the product of burning uranium in the presence of excess oxygen. Salbu also looked for uranyl carbonate, which would be formed by weathering of U3O8: they were unable to verify or to rule out its presence. Physchim62 (talk) 12:55, 23 March 2006 (UTC)
thread_title:  Born Harber cycle 

message: Flame temperature data. --James S. 20:14, 17 March 2006 (UTC)
replies: text: 2570K is the highest combustion temp that I can see in this reference. Of what pertenance to Cd's calculations can this be? At best it would seem to imply that any UO3(g) that's formed from compustion in open air wouldn't make it past the flame boundary before condensing, if that. --DV8 2XL 21:55, 20 March 2006 (UTC)
replies: text: The point is that it's above the 2000 K point at which U3O8 continues to burn. --James S. 23:23, 20 March 2006 (UTC)
replies: text: Not at 1 atm. - it decomposes at 1573.15 kelvin - to UO2 which is a solid to 3100.15 kelvin. Numbers aren't there James. --DV8 2XL 00:28, 21 March 2006 (UTC)
replies: text: If that were the case, then UO2(s) would comprise more than 25% of the particulate combustion product, and U3O8 less than 75%.  What source are you using? --James S. 00:37, 21 March 2006 (UTC)
replies: text: A lot of the final product will come from the cooler parts of the combustion enveolpe - this is more due to the physics of the flames geometry than the chemistry. I got the numbers from my Rubber Bible. --DV8 2XL 02:13, 21 March 2006 (UTC)
replies: text: So, what does your rubber bible say that U3O8 decomposes into, and what source does it give for that temperature? --James S. 16:41, 21 March 2006 (UTC)
replies: text: The decomposition product is UO2: the temperature is consitent with the NIST thermodynamic data for the two species (even if there are far too many sig. figs.!). Physchim62 (talk) 16:31, 22 March 2006 (UTC)

text: Kinetic and thermodynamic products at different reaction conditions can differ a lot! Thermodynamic reactions can be favoured but because of the reaction partners or a sharp drop in temperature where the activation energy for the exothermic reaction is no longer present they can be kinetically hindered. So U3O8 or UO3 what are they kinetical or thermodynamic products and at what temperatures under what conditions. Without all the data, asuming  which of them is in the burningproducts in gas phase of DU, is speculative or even missleading! The only thing which is shure is that nobody ever detected UO3 over burning DU (Yes Ackermann showed it but only as best presumption he could make, because he had no MS of his gas phase). Only as endproduct of the burning as solide. So state this and leave the rest as speculation, what it realy is!--Stone 09:59, 21 March 2006 (UTC)

text: Which is why this whole line of inquiry is perilously close to violating WP:NOR, Like Stone is saying; withhout hard clear references we are moving into specualtion. --DV8 2XL 15:15, 21 March 2006 (UTC)
replies: text: In fact, Salbu et al. (2005) did detect UO3 in combustion residues.  This is not speculation or original research, the fact of UO3(g) is supported by an abundance of sources from the scholarly and peer-reviewed scientific literature.  The irony of being asked for "hard clear references" is palpable. It is clear from the edits to this page that those wishing to downplay or suppress the reality of uranyl compounds as aerial combustion products of uranium have no better familiarity with the  scientific literature than some of them do with the English language. It is not my responsibility to prove verification of sources I have already verified, and I doubt it is my responsibility to try to understand the tortured ambigious spellings and grammar as have recently become so plentiful here.  However, that doesn't mean that I won't continue to try, because I think this is important, and the practice is good preparation for real-time debate, and it's like shooting fish in a barrel. --James S. 16:41, 21 March 2006 (UTC)
replies: text: In fact, Salbu et al. (2005) did detect UO3. This is fully right and this fact was never disputed! But this is not a gas but a solid particles as you can read in the abstract! So this is no proof for the gas, give proof for gas at normal conditions!--Stone 16:58, 21 March 2006 (UTC)
replies: text: Actually, this is disputed: Salbu's results are equally, if not more, consitent with U3O8 as the solid product formed from the munitions dump fire. Physchim62 (talk) 16:31, 22 March 2006 (UTC)

text: Again, Wilson (1961) p. 213. The statistical dynamics involve the number of gas molecules unable to glom onto others before reaching open air; this number is some fraction, not zero. --James S. 17:58, 21 March 2006 (UTC)
replies: text: The pressure of Iron over a pice of iron is not zero eiter but nobody would say it is a amount which has any significance. Even above ice there are a lot of molecules of water present. If going 200°C below freezing point like on titan you find no water in the atmosphere at all. mare than 500°C below the point you can detect it you will find molecules in gas phase but if you inhale all the air from Uranium trioxide for years you would not get more than drinking a glas of mineral water. --Stone 08:15, 22 March 2006 (UTC)
replies: text: You said something about raman spectroscopy. This is not a MS methode at all it si a spectroscopy methode determine the fibrations and flexing in a molecule, but it is not suitable for determining the molecular mass of molecule. But if you have a good raman spectra of a UO3 at standart conditions this would also qualify as source for UO3 gas. --Stone 08:15, 22 March 2006 (UTC)
replies: text:  Please stop quoting willson, because if you dont stop I have to give back the compliment you made: Do you ever read what you are quating?
Willson has done no research on UO3 he only quotes the ackeman paper nothing more. --Stone 08:53, 23 March 2006 (UTC)

text: You mean, other than actually burning uranium and measuring the gas condensates by observation of crystals? --James S. 10:17, 23 March 2006 (UTC)
replies: text: The page 213 you always revere to is basically a quote. And the rest of the paper deals with the real burning products of uranium not mentioning UO3 as significally imortant any more.--Stone 10:42, 23 March 2006 (UTC)
replies: text: And Salbu's similar description of UO3-rich condensates? --James S. 11:25, 23 March 2006 (UTC)
replies: text: As stated in some older publications U3O8 was contributed as UO2+2(UO3) so U03 rich says nothing. U03 solide is not ever questioned the gas is the problem! --Stone 11:35, 23 March 2006 (UTC)
replies: text: Salbu's description were of particles in which the oxidation state of uranium was +5.5±0.5: this is more consistent with U3O8 (oxidation state +5.33) than UO3 (oxidation state +6). This also fits with the normal description of U3O8 as the product of burning uranium in the presence of excess oxygen. Salbu also looked for uranyl carbonate, which would be formed by weathering of U3O8: they were unable to verify or to rule out its presence. Physchim62 (talk) 12:55, 23 March 2006 (UTC)
thread_title:  Comments on the Born Harber cycle 

message: So is there any shred of a doubt in anyone's mind that UO3(g) is NOT a factor in uranium combustion in open air? Can we put this to rest, and remove its mention from the article now? --DV8 2XL 19:11, 23 March 2006 (UTC)
replies: text: Absolutely not.  Wilson (1960), Cotton (1991), and the spectrographers following Wilson, all make it abundantly clear that uranium trioxide gas is an aerial combustion product of uranium.  You have shown no evidence to the contrary, and your attempts to use sublimation proportions to represent combustion product formation are easily shown as abject fraud. --James S. 17:52, 24 March 2006 (UTC)
replies: text: You have had every one of your arguments shredded. People have gone to great lengths to explain the science and do the calculations to demonstrate that your contention that this gas is a factor is without foundation. You have not defended yourself with any arguments other than references that further prove you wrong. There is no scientific or rational reason that this topic should be covered in this article. You continued forcing of this issue only serves to underline your own ignorance of science and your contempt for the process here at Wikipedia. --DV8 2XL 18:18, 24 March 2006 (UTC)
replies: text: Who has countered the equations of Wilson (1961)?  Who has countered the plain statement of Cotton (1991)?  Have you personally even gone to the library once to research these questions?  Simply saying sublimation formation is the same as combustion formation is absurd, no matter how many times it is repeated, or by how many people. --James S. 19:26, 24 March 2006 (UTC)

text: Following WP:BOLD I have reworded the section to include a discussion of UO3 but to downplay the gaseous phase (which has been shown to not be persistent). zowie 18:30, 24 March 2006 (UTC)
replies: text: With all due respect Zowie the article is about UO3. The Issue is if it exists in a gaseous form and if that gas is formed in any meaningful amounts when uranium metal burns in air. I believe that the discussions above indicate that it doesn't. Any mention of this gas in this article cannot meet Wikipedia's criteria for notability or verifiability and in fact violates the WP:NOR rule because of that. --DV8 2XL 19:03, 24 March 2006 (UTC)
replies: text: Your beliefs are unsupported by sources.  Look at the thermodynamic enthalpies of formation:  UO3 is a much more likley product than UO2, which is 25% of the solid product.  You haven't shared a speck of evidence that the crystalization observed by Wilson (1961) and Salbu et al. (2005) isn't according to the equation given by Wilson.  You would rather point to a discussion of vapor pressure?  Water vapor condenses at STP, too.  Will you claim, therefore, that steam "cannot meet Wikipedia's criteria for notability or verifiability" as a product of boiling water? --James S. 19:26, 24 March 2006 (UTC)

text: Hmmm... I guess I should chime in then to your original comment -- I have not yet seen (on this page) a convincing argument that UO3 is not important in uranium combustion -- only that it is not an important final product of that combustion.  I thought that part was resolved.  I guess I'll step back from this one -- feel free to revert... :-P zowie 19:20, 24 March 2006 (UTC)
replies: text:  I see the problem now - James seems to think that the laws of thermodynamics do not apply to combustion or that UO3, once formed, will not condense (or both). 129.215.37.180 02:40, 25 March 2006 (UTC)
thread_title:  O.K. 

message: ===molecule structure===
The structure from Gmelin of the molecular UO3 is from deep temperature matrix experiments. UO3 is incorporated of a solid argon matrix which is inreactive against nearly everything at low temperatures.  The Raman and IR spectroscopy date suggest that the linear UO22+ with a O2- on the side which gives T-shaped molecule. The trigonal planar (D3d) structure was also proposed but only favoured by calculations. The T-shape is only estimated by the symmetry of the vibrations shown in Raman and IR. 
(Comment for James: Raman is no MS spectroscopy, it is comparable to IR spectroscopy) 
The deep temperature argon matrix experiments are the state of the art experiment for instable molecules to be detected. In the matrix the molecules can not react with each other because they are separated by inreactive noble gas molecules und the necessary activation energy is not available at deep temperatures. (kinetically and thermodynamically hindered reaction conditions)  The concentration of molecules can be high, because of that  Raman and IR are able to detect them.
: The calculations are from the Pykko paper, right? No idea how good his basis set was (and with uranium one must take relativistic effects into account!), besides C2v is D3d minus the threefold, and I have no clue how easily the molecule is deformed when in a solid matrix. Anyway, I have added a paragraph on the gas-phase structure now.
===Structure in solid state===
X-ray crystal structure is only possible for the solid and shows for gamma UO3 two types of uranium atoms the hexa (octaedric) coordinated in. 
The structure can described as UO22+ UO42-.
In beta UO3 three types of uranium atoms are present. Two forming Uranyl with four oxygens in bigger distance. One with a octaedric surrounding and two with a octaedric surrounding connected over one oxygen. Which gives a 
2(UO22+) UO42- U3O72-
as a good suggestion. 
: I have now put the sum formula for the gamma phase in the infobox. Not great, but better than having a structural formula for the single molevule as before. A diagram of the solid state structure would be best. 129.215.195.81 18:25, 28 March 2006 (UTC)
replies: text: Well, at least they have a vapor pressure. It's a start. 129.215.195.81 18:25, 28 March 2006 (UTC)
thread_title: structure

message: X-ray crystal structure is only possible for the solid and shows for gamma UO3 two types of uranium atoms the hexa (octaedric) coordinated in. 
The structure can described as UO22+ UO42-.
In beta UO3 three types of uranium atoms are present. Two forming Uranyl with four oxygens in bigger distance. One with a octaedric surrounding and two with a octaedric surrounding connected over one oxygen. Which gives a 
2(UO22+) UO42- U3O72-
as a good suggestion. 
: I have now put the sum formula for the gamma phase in the infobox. Not great, but better than having a structural formula for the single molevule as before. A diagram of the solid state structure would be best. 129.215.195.81 18:25, 28 March 2006 (UTC)
replies: text: Well, at least they have a vapor pressure. It's a start. 129.215.195.81 18:25, 28 March 2006 (UTC)
thread_title: Structure in solid state