The Chemical Species of the Elements Resulting from An

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THE;CHEMICAL SPECIES OF THE ELEJJENTSRESULTING FROM AN ATOMIC BOMB DETONATIONIN AIR

L. R. Bunney and N. E. Ballou

UNCLASSIFIED------i .

This documentconsists of 32 pages. This is copy&$? of 290 , Series A.

UMCLASSIFIED------

THE CHEBIICALSPECIES OF THE ELEKEMTSRESULTING FROM AM ATOMIC BOMB DETONATIONIN AIR

L. R. Bunneyand N. E. Ballou

Final Report

TechnicalObjective AR-7

ChemistryBranch C. R, Schwab,Head

ChemicalTechnology Division E. R. Tompkins,&ting Head

U. S. NAVAL RADIOLOGICALDEFENSE LABORATORY San Francisco24, California

ScientificDirector WilliamH Sullivan

25 ?.!ay1951

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Date issued: 2 August1951

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ABSTRACT

EstMtes have been made of the cheaicalnature of the productsof an atomicbomb detonationoccurring in air. A discussionof the relevantdata and necessaryasstunptions is included. Based largelyon thermodynamicdata, the rmults ind:icatethat these productsshould exist mainly as the oxides. Thus, with problemssuch as those of co&&nation and decontaminationin which chemical,properties aze a factor,the behaviorsof the variouselements under a varietyof conditionscan be predicted.

______UNCLASSIFIED 6.

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THECHEMICALSPECIES OF THE ELEMENTSRESULTING FROMAll ATOMIC BOMB DETOMATIOH IN AIR

L. R. Bunney and B. E. Bsllou

INTRODUCTION

The chemicalnature of a contaminantis of importancefor studiesof its contaminationand decontaminationbehavior. This report presentsan estimationof the main chemicalspecies of the variouselements to be ex- pectedfrom an air detonationof an atomicbomb. The reactionsconsidered are thus mainly dry, althoughthe possibleeffects of atmosphericmoisture are discussedto some extent. (A similarstudy of the chemicalnature of the productsof an underwateratomic bomb detonationhas been started.)

A detailedand accurateanalysis is impossibleowing to the lack of sufficientexperimental data on the type of reactionsinvolved, and also becauselrnrch inf'ormation concerning the atomic cloud is lackingat present. This report presentsa best estimatebased on the availabledata and a seriesof bold assumptions.The authorsare at presentplanning experi mental tests of some of the hypothesesused in this report.

The elementsunder considerationare the bomb materials:iron (since the compositionof the steel was not accuratelyknown, such things as small peraentagesof nickel,manganese, etc., were estimatedfrom the composition of armor plate);;uranium or plutonium;conventional explosive products: carbon,nitrogen, hydrogen and oxygen;and the fissionproducts from zinc, atomicnumber 30, to gadolinium,atomic number 64.

The report is comprisedof a discussionof the assumptionsinvolved; a table listingthe elementsand their estimatedvedominant chemicalspecies; a sectiondevoted to brief outlinesshowing how we arrivedat the data listed in the table,with referencenotes; a short conclusion,in which the possibleeffects of nuclearreactions (not consideredin the analysis)are pointedout; and a bibliography.

DISCUSSIOlVOF ASSlJlWTIOl'?S

It is necessaryfor even a rough type of calculationto assume that certainrelative percentages of constructionmaterial, such as iron, uranium or plutonium,and fissionproducts are presentafter the detonationof an atomicbomb. I:tis consideredthat even a ten-folderror in any of these estimateswould not seriouslyaffect the conclusionsin this report.

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The analysisis limitedto Ahighaair bursts,i.e., ones in which the actualdetonation occurs at or above 500 feet from groundlevel, which resultsin no appreciale vaporizationof soil materialor mixing of soil with the ball of fire.P Such altitudesprevent rapid coolingof th3 ball owing-tothe expenditureof energy in vaporizationof soil material and, hence, equilibriumconditions are more closelyapproached in a given temperature range.

The volume of the vaporizedbomb materialsand productsis an important consideration.This ll~t~ estimatedby a rough calculationfrom data on the size of the ball of fire as a functionof time after detonation.1At one secondafter detonationits volume is approximately1 x lOlO liters,

The considerationof the amountof mixing of the surroundingatmos- phere, in the first ten seconds,was of the utmost importance.The data in (1) and a mathematicaltreatment by Taylor3indicate that the degreeof mixing shouldbe very large, even in the first two secondsfollowing the detonation. A rough calculation from an applicationof Taylor'stheory b Cohen,Hirschfelder, et.,4 showedthat a most conservativeestimate of the amount of air zdxed with the ball of fire in the first two secondswould contain103 times as much 02 as would be necessaryto react all bomb material to the highestoxidation state possible. The conclusionis that the amount of air presentis not a limitingfactor in a reactionof the bomb materialsand products,and that, of the possiblechemical species of the variouselements present, the oxidesend nitridesshould be by far the most important.

In some cases,the nitridesof the particularelement were knowu to be pointedout b Kelley,5 ZrK is the most stableof the metallic Rungh equilibriumcalculations at 2500°Kusing the data of no appreciableamount of ZrK in equilibriumwith KroZ at atmosphericconcentration3 of N2 and 02. Similarcalculations for other elementsinvolved show similarnitride concentrations at equilibriums.of course,the equilibriumconstants for the formationof oxidesfrom nitrides in air increaserapidly with decreasingtemperature. The conclusionis that the oxides are the most importantchemical species present in most cases, althoughtraae concentration362 percentor less) of nitridesare possible in some cases. Hence, the estimatesin Table 1 are not meant to preclude the possibilityor even the probabilityof the formationof some unmentioned compoundsto the!extent of 2 or 3 percent. In some cases,compounds which are thoughtto cmur only in such quantityare mentionedin the table because of our convicti6nsof their probablepresenae.

Generaleqrtilib~ium considerations9 show that in most cases appreciable compoundformation does not take place much above 5O@K, she above that temperaturemost elementsexist as zaseousatoms or ions. This temperature is reachedapproximately one second-afterdetonation of a nominal (20,000

______CLASSIFIED ------_---__UNCLASSIFIED ton TDT equivalent)atomic bomb.1 Just below this temperature,most compounds are thoughtto be only diatomicin nature (i.e.,only compoundsof the type FeO,UC, F'uO,etc., are formed),but on coolingfurther oxidation is achieved. In the cases of those elementsfor which oxidesare predicted, the particularoxides resulting should be those which are thermodynamically most stable. However,it is known that in some cases the rate of reaction is slow where.transitionsoccur betweenoxides of an element (e.g., FegO4+Fe203);11hence, the oxide of the elementwhich predominantlyresults at,roomtemperature should be the one which is thermodynamicallystable at the lowest temperatureat which equilibriumis attainedfairly rapidly. FPhereinformation was lackingon such transformations,qualitative state- ments in referenceworks were interpretedin a rough quantitativeway. In a few cases,the best interpretationis the existenceof a mixtureof two or more possiblespecies; it is probablethat the compositionof the mixture would be dependenton the coolingtime in significanttemperature ranges, and such other factorsas pressureof 02 and particlesize.

The effectsof the ultravioletradiation resulting from the detonation of an atomicbomb are considered. The availabledata1 show that this type of radiationis :small when the ball of fire has a temperatureof about 50000g. Below 5000°K,the amount of ultravioletradiation decreases very rapidly,approaching zero at about 400009. As has en pointedout, very little compoundformation is possibleabove 5OOOoK.B" Hence, the ultraviolet radiationis consideredto have,a negligibleeffect.

It is thoughtthat the radiationfield of the fissionproducts, which is of longerduration than the ultravioletradiation, would have a definite effect. This is consideredin the paragraphon silver. Other compounds which undergophotoelectric decomposition would be similarlyaffected. How- ever, no evidencehas been found for this type of reactionin the other com- pouudswhich are consideredto be possiblespecies.

No attempthas been made to evaluatethe %alence inductivity"effect reportedw Selwpodl4although it shouldbe pointedout that this may be exhibitedto a large extent in the fissionproducts owing to the small par- ticle size and large proportionof iron expectedto be present.

The effectsof solid solutionswere not evaluatedbecause of the lack of availabledata. The problembecomes quite complicatedif all the PoSsi- ble constituentsare considered. Each elementhas been treatedindividually in this report. However,the possibilityof formationof compoundsbetween basic and acidic oxidesshould be considered. In many cases (selenites, tellurites,gerzanates, stannates, arsenites, antimonites, carbonates, nitrates,silicates, phosphates, sulfites, sulfates, molybdates, and in some cases even ferratesand uranates)the formationof such compoundsis thermodynamicallypossible.

QJCLASSIFIED----_-_--- 9. * ______UNCLASSIFIED The factorsaffecting the formal&m of such compoundsare: concentration of the reactants;rate of coolingin the significanttemperature range; amountand type of surfaceavailable; adsorption of gaseousspecies by con- densed species;rate of formatfonof the compounds;and in many cases the presence or absenceof appreciableamounts of water. Many of these factors are eithernot known at presentor are not sufficientlywell known to be useM. in predfctingthe resultsto any reasonableorder of magnitude.

Generalstatements as to the likelihoodof the formationof certain anionsare includedin the appropriateparagraphs in the body of this report, but the discussionof the formationof specificcompounds is limited to the very few well known cases. These are to be found in the paragraphon the elementwhich forms the cation.

Lastly,an assumptionis made of stronglyoxidizing conditions in air for the elementsconsidered. In certaincases9 it is thoughtthat there is the posaibilityof incompleteoxidation owing to entrapmentof minor elements in larger :pticles of major constituents.This effect is considered to be a minor on3. It has been necessaryin many cases to extrapolate thermodynamicdata beyond the point where it is reasonablyaccurate,' but the trends shown are felt to be significant. 10.

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TABLE1

Atomic No. EstimatedPredominant Suecies (Expectedlesser speciesIn parentheses)

1 Hydrogen Hz0 6 Carbon CO2 7 Nitrogen N2" 8 Oxrgen 02# l-4 silicon ST02 or Silicates 15 Phosphorus P2O5 or Phosphates 16 sulfur SO2(SO3)or Sulfites(Sulfates) 24 Chromium cr203 25 Manganese rn304 26 II-on Fe304 (Fe2031 28 Nickel NiO 29 Copper CllO 30 zinc ZnO 31 Gallium Ga203 32 Germanium Ge02 33 Arsenic As203 34 Selenium Se02 35 Bromine &c (I&, b2) 36 Krypton Kr 37 Rubidium Rb02 (RbI,RbBr, RbOH, Rb2CO3) 38 Strontium SrO (Sr(OH)2,SrCO3)

* Note: Of importanceto the opticalproperties of the .ballof fire is the formationof oxides of nitrogento the extent of roughly100 tons in an air burst. The equilibriumconcentrations of nitric oxide and nitrogen dioxidein the air are from one to five percentfor temperaturesbetween 2000°C and 5000c'C;the equilibriumconcentrations are negligiblybelow 2000°C,and above 5000°Cthe oxidesare dissociatedinto atoms.

+* Note: Small amountsof ozone are probablyformed to an unknown extent in an air burst of an atomicbomb.

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3.2.

DATAAlVDIBFF3ENCES

The thermodynamic data699indicate that the only possiblespecies is H20.

The thermodynamicdata6s8,9 indicate that CO2 is the only important species. CO is thermally the most stable of the carbon compounds and it i8 oxidiaed to CO2 at lower temperatures.9

nitrogen and oxygen are considered in connection with each of the other elements. Other than the compounds mentioned in the other para- graphs, the oxides of nitrogen, nitrates and nitrites are considered to be the only possible species. The data in %ffects of Atomic Weapon& indicate that there is a large quantiy of HO formed between 2000% and 5000°iS, but this amount would be rapi dYIy decomposed as the temperaturedropped below 2000°K.

The f,ormationof most nitratesand nitritesis not thermodynamically possibleunder the pertinentconditions until the temperature drops below 1000°K. Since at this temperaturethe concentrationof I!0 and 80 are decreasingdru, to decompositionand diffusionand the ra P e of reactionis probablyquite slow, the probability of nitrates and nitrite8 being present a8 significant resulting species is considered to be very small. Hence, the nitrogenand oxygen other than - that combinedwith the other elementsis considered to be in the elemental state when at the temperatureof the atmosphere.

There are two known oxides of ailiccn, SiO 8nd Si02.7*10911 913 SiO is only obrtained w drasticreduction of Si02.7911SiO is very stableand is the usual oxidation product of the element. 721Y 3

The data of Brewer, Bromley, Gillea and Lofgren7r8indicate that the nitride should no$ be present to an aweciable extent,

Th8 th8rIBodynamiC data7,17,20,21 indicate that the bromide8 and iodide8 should not ocuur to more than one percent* of the silicon.

There is a very good possibility of silicate formation, but the extent is thought to be unpredictable.

* The phrase "should not occur to more than one percent” used here and with slightly different wording snb8equently only establishes an upper limit. The species may not occur at all. 13.

--______-UBCLASSIFIED The differencebetween actual silicateformation and solid solution of SiO2 with one or more basic oxides is difficultto deftie. Sufficeit to isay then that the final resultingspecies is considered to be SiO2 either in solid solutionwith otner oxidesor actuallycom- bined with bas:icoxides to form silicates. P Phosphorushas three known oxides,P2O3, P2O4 and P 05.10911913 In excessair, the lower oxidesare oxidizedto P2O5.10,21,13 P2O4 is only produced'by heating P2O3 in a limitedamount of air.11913 P2O3 is oxidizedto P 05 in excessair even at 5O-60OC.13 P2O5 is stable even at 17OOoK,13 and, hence, is concludedto be the major resulting species.

In general,the likelihoodof the formationof variousphosphates is consideredrather small unless one brings in the effectsof moisture. In that case, neutralizationof the phosphoricacid formedfrom the P2O5 would give phosphates. This neutralizationmight be limited in extent,as far as materialsresulting from the detonationare con- cerned,by volatilityof P2Og (sublimesat 347oCl9),which couldbring about a physicalseparation from many of the basic oxides. However, phosphoricaci.d would be formed in the presenceof moisture,and neu- tralizationlq other basic compoundsis possible.

The thermodynamicdata 6312 indicatethat the nitride,P3N5, shouldnot be presentto an appreciableextent.

The thermodynamicdata6,12,17,20,21 also iudicatethat the bromides and iodide8should not be presentto an appreciableextent. s The only importantoxides of sulfurare SO, SO2 and SO3.6,10,11,13 The othersneed not be consideredhere since these are the only ones which are obtainedw oxidationin air.10,11913SO is only obtained at low pressurein air.13 It is thoughtto be a possiblehigh temperature species,but shouldbe oxidizedto SO2 on coolingto temperatures of about 3OOOo-40000C.SO2 is the usual productof oxidationin air,lO,ll,l3alth ough SO3 is the thermodynamicallymore stableat room temperature.6,36 However,at temperatures(below 1000°K) at which SO is more stablethan SOS, the rate of oxidationis rather slow.10~11~13 The rate is speededup by surfacecatalysts such as Fq03.10,11,13 It is thoughtthat a mixtureof the two oxideswould result in the case under considerationwith SO2 predominating,but the compositionwould be a functionof the concentrationsof the gases, amount of available catalyst,and of the rate of cooling. The low concentrationfavors SO2 formation.

SO2 and SO3 might very well react with some of the basic oxides to give sulfitesand sulfates,especially in the presenceof water.

UNCLASSIFIED______14.

EECLASSIFIED--_-_----_ In general,these reactionsbecome thermodynamically possible at about 1000°K. The situationis similarto that with other acidic oxidesin that physicalseparation may occur to some extentand the rates of the possiblereactions are not well known.

Nitrogensulfide, the most commonof the nitrogenand sulfurcom- pounds,is endothermicand is thoughtto be metastable.13

The thermodynamicdata6,17,20,21 indicate that the bromidesand iodidesshould not be formed to an appreciableextent.

Cr here are three well known oxidesof chromium,CrO, Cr203 and CrO3.;T 97910J1913 CrO is easily oxidizedto Cr203 in air13 and may only be a solid solutionof metal and Cr203.7 Cr203 is uite stable,697and is the usual oxidationproduct in air.10,~1,13 CrO3 is decomposedat about 5400K,7and about 70009 the decompositionproduct is Cr*03.7 The intermediateproduct may be a solid solution.

The nitride,CrN, decomposesat about 177OOK. The thermodynamic data69798indicate that it shouldnot be formed to an appreciable extent.

The thermodynamicdata 6 97 917,*0,*1 indicatethat the bromidesand iodidesshould not occur to an appreciableextent.

!D There are four known stable oxidesof manganese,bh0, Mn304, Mn2O3 and MnO2.7,10,11,13 &lo can be readilyoxidized to the other oxides in varioustemperature ranges. 7,10,11,13 At room temperature, MnO goes to blnO2in air, if the oxide is finely divided,13but no evi- dence is availableon similarreactions for the higher oxides. MnO2 decomposes,to k2O3 at about 5350C.19 Mn2O3 decomposesto Mn304 at 108ooc.15,1'3Mn304 does not seem to oxidizefurther on cooling. Hence, Mn30.4is consideredto be the probableresulting species.

The thermodynamicdata 6,7,S indicatethat the nitridesshould not be presentto an appreciableextent.

The bromidesand iodidesare indicatedby the thermodynamic data6,7,17,*0,*1not to be presentto more than one percentof the manganese.

Fe There are three known stableoxides of iron, FeO, Fe304 and Fe203.7,10,11,13Th e equilibriaamong these is discussedby Darken and Gu,rry.4,7,48At 14OOOC there is a free energy of -54,500Cd for the reaction of 2Fe 04:+@2+3Fe203 as written.I$ Fe0 fS easily OXi- dized7,10,1.1,13,47,28and is not thoughtto be a possiblespecies, The thermodynamicdata6,7,47# indicatethat Fe203 shouldbe the

UNCLASSIFIED-----W---B-- 15.

EECLASSIFI---__-__ --ED major resultingspecies ff equilibriumis approachedbelow 15oooK. However,the compositionis dependenton the partialpressure of oxygen and the coolingtime. Latimerand Hildebrandstate that the rate of oxidationof Fe304 to -Fe203is slow.ll

The nitridesof iron are metastablegand are not consideredto be possiblespecies.

The bromidesand iodidesare not thoughtto be presentto an appreciableextent according to the thermodynamicdata,6,7,17,20,21 but also me not possibleto any appreciableextent because of the relativelysmall amountsof the halidespresent with respectto the amountof iron present.

The ccnclusionis that Fe304 shouldbe the main species,but smalleramounts of Fe203 are possible.

U The only oxide of nickel known as a singlepure phase is Ni0.7 Otherswhich vary in compositionfrom NiO to H202 are claimed,ll&3 but are usuallyprepared in solution11or as surfacefilms.14 Ephrai& claimsthat NJ1304gives off oxygento form NiO at about 24oOc’0 0nl.y Ii0 is preparablefrom the elements.7,11&3

No stablenitride of nickel is kn0wx-1.~Therefore, it is not consideredto be a possiblespecies.

The thermodynamicdata 6 97 917,20,21 indicatethat the bromidesand iodidesshould not be presentto an appreciableextent. cu Copperhas two known stableoxides, Cu 0 and Cu0.10~11~13When oxidizedin air, the usual productis CuO,la ,11,13which decomposesto Cu20 and oxygen,on heatingto about 1026% in air.l5&9 However9 on cooling,C1120 is oxidizedback to CuO.

The nitridesof copperare metastableb$ and are not considered to be possiblespecies.

The diiodideis not a possiblespecies, since it is not stable.17 The dibromideis indicatedby the thermodynamicdata6,7,17,20,21 to be a possiblespecies. The monobromideand monoiodideare, ibo, poSSi- ble. Thermodynamicconsiderations6,7,17,20?1 show that altogether they shouldnot be presentto more than one percentof the copper. zn Zfnc is readilyoxidized in air to ZnO, the only known oxide.lo,u

Zinc nitride,Zn3N2, is metastableSand hence is not considered to be a possiblespecies.

------.---UNCLASSIFIED 16.

The data of BrewerlT$O indicate that with concentration considerations the bromides and iodide8 are not possible to more than one peroent of ihe total ainc present.

Ga203 is the most stable oxide and the oxidation aroduot of the metal in air. 6,10&l GaoO is known.I but is unstable ;ith respect to Ga2O3and gallium metal.11

The thermodynamic data6p8,12 lead to the conclusion that GaB should not 1~ present to a greater extent than one percent of the total amount of gallium.

The thermodynamic data6917920 indicate that it is not possible for more than one percent of the total gallium present to occur as the bromides or iodides.

GeO and Ge are known; germaniumand GeO are readily oxidized to Ge$ in air.l0,3&3

The nitride, Ge3R4, is metastable and, hence, should not occur.

It is felt that, because of the considerations mentioned in the Disouseion, germanantes could not be a very important species for this element, although it is a possible one in a few cases.

Rough equilibria data6 917,20,22 indicate that the bromides or iodide8 should not be present to a greater extent than one percent of the germsninm.

As203 and As205 are the two known oxides of arsenic.1°,11,13 Al- though As205 is thermodynamically st ble at room temperature, it decomposes to As203 and @ at 588Sr. f 9 Ehen the element is burnt in air, fairly pure As203 results .l”P

The nitride, Ad!, has a heat of formati n of between + 7 and + 35 kiloealoriets per mole. 6918 It is not stable 8 and is not considered to be a possible species.

As20 is not thermodynamically stable above 588og; thus, combi- nation ui 2h other oxides is probably slow owing to the low temperatures required. As203 is quite volatile (sublimes at 193OC) and, hence, might be physically separated from other oxides. lost arsenites (particularly those of iron) decompose at low temperatures. Therefore, the probability of srsenite or arsenate formation is considered to be very small. The presence of appreciable amounts of moisture would increase the probability of such reactions, but the extent is difficult to predict.

--11------1-UECLASSIFIED 17.

I------UICLASSIF --_IED The bromides and iodidesshould not b8 pr8S8ntto more than one percentOf the arS8niC.6,17,20,21 se Se02 iz3the only known oxide of se enium which is thermodynamically stableunder ordinaryconditions. B ~1~911913

Seleniumnitride, SeAlVA, explodes at 200o~,1549 and hence is not thoughtto be a possiblespecies.

g818nitesof heavy metals decomposeat ratherlow t8mp8ratur8S16 and, While 'thoseof th8 alkali and alkalineearth metals are possible, it is felt that concentrationconsiderations preclude the possibility of their formationto an appreciableextent.

The th8rmodynamicdata 6 917~~~ indicatethat less than one percent of the sela1iumpresent should occur as bromidesand iodides.

The case of bromineis complicatedsomewhat by the fact that many of the bromidesof the elementsinvolved in this discussion e not stable at temperaturesat which the correspondingoxidies are. 2 ,7,*?7 It is also felt that much of the bromideformation would be prevented by the Etch larger concentrationof 02 (and h8nC8 the oxide would b8 formed in many cases in preferenceto the bromide). F'urthermore,all oxides of bromine are unstable at ordinarytemperatures.6~10~ll

It appaars that the bromine will to some extentreact with elements with Which it can form bromides(e.g., Rb and Cs), with a distribution among the elementswhich is very difficultto predict.

It also seems quit8 likely that a small portion will not react in this manner and ati1 cool out Fn the elementarystate. In this connection,it shouldbe pointedout that IBr is thermodynamically more stable than either m or 12.I7 Therefore,since there is a similar situationwith iodine,some of the mixed halogen (IBr) shouldresult.

In the specialcase of the reactionwith silver,which is thermodynamicallypossible because of the comparativeinstability of gg20,6,17it is thoughtthat much of the halideformed would be decomposed by light and gamma radiation.

. It is felt that addition compounds of the typ8 MOBr (whereM standsfor any divalentmetal) or any other oxybtiideare eithertoo unstableto: b8 significant,lo or the rate of formationiS too Slow t0 form an anreciable amount.35

Krypton,because of its lack of chemicalreactivityl0&1,24 is concludedto b8 in the element& State.

_-_------UNCLASSIFIED PbE&ASSIPIED____-___ Rb Rubidiumvesents one of the more complicatedcases consideredin this discussionthus far. There are four known oxides of rubidium, Rb20,R 0 Rb203, Rb02 (Rb204),as well as possiblesubox- ides.T,lb8, ff .$3 The suboxidesare only preparedunder conditionsthat are not pose.iblein the situationunder consideration.11RI@& has by treatingliquid ammonia solutions of the metal Since RbO2 is the productobtained by ignitionin felt that it would be the chief productin the case The alkalimetals have a eater tendencyto form higher oxideswith increasingatomic number; F3 hence, in rubidiumthe ~~&de~~;s very great. In excess oxygen,it shouldreadily oxidize .

Rubidiumnitride, Rb3N, is decomposed.above68WK,S and hence shouldnot be a possiblespecies.

RbO2 decomposesat rather low temperatures,7as do the other oxides of rubidium,7,15,19$3w hereas the bromideand iodideare quite stable at high temperatures2o (above3000°K)c This leads to the con- clusionthat the bromideand iodideshould be importantspecies in the case of rubidium. The iodideshould be more important,than the bromide becauseiodine is presentto about twice the extent of brominein the time availablefor reaction.22 Since there is enoughhalogen to react with only about one-halfthe alkalimetals,22 the latterwill also form their oxides.

In the cases of Rb, Cs, Sr, and Ra, the possibilityof formation of hydroxide,bicarbonate, and carbonateshould be considered.

and CO2 are usuallypresent in comprisesabout one percentof order of O-03 - 0.05 percent.11

These amountsare such that the formationof hydroxidesand carbonatesare thermodynamicallypossible 6:7,12,52 at temperaturesof the order of 1000°K and bicarbonatesat about 4OOoK. However,it should be pointedout that the rates of reactionto producethese COD- pounds are not well known. Also, high temperatureforms of oxides which are very unreactive(e.g., "dead burnt" CaO and MgO) are quite numerous.13

For these reasons,the exact resultantspecies of these elements are almost impossibleof prediction. They may also vary with length of time followingthe burst. Sr Strontiumis known to have only two oxides in the dry state,SrO and Sro;!.l",ll&3Sr02 is only preparedunder high 02 pressureand

____UNCL ______ASSIFIE 2 19.

______UNCLASSIFIED

decomposesat ~$88~ to s&7 Hence, it is not a possiblespecies.

Strontiumnitr de, SrgN2, decomposesat temperaturesat which SrO is stablet.a air.79 8 Consequently,it is thoughtthat the nitride would not be presentto greater than one percentof the strontium.

The data of Brewer7,17,2°,21sh ows that the halidesshould not be presentto more than one percentof the strontium.

For discussionof the possibleformation of hydroxides,carbonates, and bicarbonates,see the paragraphon rubidium. x The only known oxide of yttriumis Y203.1°~u,37 Rough equilibriumcalculations from the data of Brewer798indi- cate that the nitride,YN, shouldnot be presentto the extent of one percentof the yttrium,if conditionsapproach equilibrium a t mpera- tures at which Y and Y2O3 are condensedphases (2500°E).189 9$1 9$3 In addition,calculations show t at the oxide is stableat temperatures at which YN is dissociated.78I

Similarcalculations for the bromidesand iodides7,17,20,21indi- cate that they shouldnot be possibleto more than one percentof the I yttrium. zz ZrO2 is the only known oxide of airconium.7,10,13 The possibilityof &IV formationis coveredin the preliminary discussionin this report. In addition,the thermodynamic data7,S921,123indicate that, if equilibriumis approachedat 25OOoK, no appreciableamount of ZrE is present.

The thermodynamicdata 7 917,2°,21,23 indicate that, if equilibrium is approachedat 2OOOOg,the bromidesand iodidesshould not be present to an appreciableextent.,

Niobiumhas three stable oxides,NbO, NbO2 and Nb20 .7,1°,a Nb203 is doubtful7and, if preparable,is relativelyuns z able compared to the other oxides. Ignitionin air of the metal or of any of the lower oxides gives Nb20 .24 Brewer'sdata7 indicatethat Nb20 is stable above 15OOoP. N4 abates are consideredpossible, but ori? y to a very minor extent.

NbN, the nitride,should not be presentto 7q sypreciableextent kom the indicationsof the thermodynamicdata. Y Y

W-W-UNCLASSIFIED ______20.

------_----UNCLASSIFIED The iodideis known to react with atmosphericoxygen to form Nb205,24and hence is not a possiblespecies. The bromideis also thoughtto be unstableat high temperaturein air with respectto I%205 and bromine. luI0 Moo2 end MOO are the two known stableoxides of molybdenum.7,10 Mc203 has been cP aimed by two groupsof investigatorsand later deniedby one of them. Anothergroup failed to find evidenceof !~!02O3.~The thermodynamicdata indicatethat of the two, Moo3 is the more stableup to a temperatureof about 20000K.6,7 Moo2 is oxidized to MO03 the oxygen of the air at temperaturesbelow about 15000K.6~b4 :124

Molybdatesare consideredpossible, but only to a very small extent.

Th niitride,Mo2N,, is not very stableand shoulddecompose near 1000og.8 Hence, it is not thoughtto be a possiblespecies.

The bromidesand iodidesof molybdenumare not stableabove 1000°K.20 Hence, they are not thoughtto be possiblespecies.

ZG Technetiumpresents a ratherunique probleminasmuch as its basic chemistryhas not been studiedto an extentthat would give much indi- cation of its most stable compounds. Accordingto the early investi- gators of 'thechemical properties of technetium,it resemblesrhenium much more than manganesein its chemicalbehavfor.25?26,27,28

Reviewson rhenium24929indicate that it has a very wide variety of valencestates, but the heptavalentstate is the most stable.

Wo groups of workers30933p34indicate the existenceof Tc2S7 as a normal sulfideprecipitate in acid solution. Inghram,Hessand Hayden31state that for some mass spectrometerwork they receiveda sample of KH4TcO4and obtainedpeaks correspondingto TcO+, TcO +, and Tc03+in the work, Fried32indicates the existenceof m4Tc 84. In later work34 it was shown that a hexavalentstate of technetium exists and that Tc04' is not as easilyreduced as MnO -. In the latter experiment,no compoundanalogous to MnO2 was $iscovered on reduction. The indicationsof the work mentionedabove are that the oxides of technetiumare possiblyTcO, Tc304,Tc203, TcO2 and Tc207 with TcO, TcO3 and Tc207 most probable. The latestwork, that of Fried and Eal1,49shows that TcO3 is the volatileoxide which was pre- viouslythought to be Tc207 by most workers. Indicationsseem to favor the formationof TcO in the case under discussion,although this needs verification.P echnetatesmay also be possiblespecies.

UNCLASSIFIED------21.

------UBCLASSIFIED Bo work has been done with the nitrides,bromides or iodides,but it is thoughtthat, as with manganese,they would not be as stableas the oxidesunder the consideredconditions.

Rutheniumhas three well-definedoxides Ru 03. RuO2 and RuO~.~O,~~ RuO d068 not appear to exist.lO.il 2% hO2 is obtainedon heatingthe finely dividedmetal in air.10$1$4 Ru04 appearsto de- composeto RuO2 at about lOOaC,I",13,19 The conclusionis that Ru02 is the most probableoxide and, since the metal is readilyoxidized in air, the most probablespecies. However,Ru2O3 is also possible.13

Bo nitrideof rutheniumis known and hence is not consideredto be a possiblespecies.8913

The bromidesand iodide8are rather easilydecomposed and, according to Brewer98data,20:21 should not be presentto an appreciable extent.

Bh des of rhodiumare known,Rh20, Rho, Rh203, Rho and and Rho2 are readilydecomposed by heat18 ,15,19,24 to be possiblespecies. Assumingreasonable entr pies, as in the method of Brewer,7917923the thermodynamic data8 912 indicatethat Rh2O3 is substantiallymore stablethan Rh20 and Rho at almost all temperaturesat which they exist. This is born out by the dissociationtemperatures under one atmosphereof 0 given by Mello&) for the three oxides,Rh20 at ll27OC,Rho at 1121'8 and Rh2O3 at Xtl3OC. Mellor also atateathat Rh2O3 is the productof oxidation in air of the finely dividedmetal between600°C and 1000°C. It would appear that Rh2O3 shouldresult almost entirelyif the cooling rate in the signiPicanttemperature range (i.elpthe temperature range at which reactionbecomes possible for rhodiumunder conditions found in ABD) is fairly slow. The elementitself is also possible, but in the ffnely dividedstate expectedit shouldbe oxidized.

As in the case of ruthenium,the nitride is not known8,13and is not consideredpossible.

The bromidesand iodide8are rather easilydecomposed10r17,20,21 and are not thoughtto be presentto an appreciableextent. cuPA The only stableoxides of palladiumare PdO and Pd02.1°~11~24 PdO2 is not very stableand decomposesto the monoxideon heatingto about 200s~. PdO2 has never been formed by heatingthe metal in air.l" Various claimsfor the existenceof Pd20 have been disproven by showingthat the productwas a mixtureof PdO and the metal.lO

---UECt~~SIFIED -_--c-w 22.

JMJCLASSIFIED______a_ The nitrideis not known8913and is not consideredto be a possible species-

The bromidesand iodidesare rather easilydecomposed1°~17,20?l and are not thoughtto be presentto an appreciableextent.

There is a very good possibilitythat the metal itselfoccur_s, becauseof the relativelysmall thermodynamicstability of PdO.c&2 However,in the very finely dividedstate expected,it is thoughtthat PdO would be the predominantspecies, although metallic palladium is also expectedto some extent, The compositionof the mixturewould depend on the rate of coolingof the metal. If the coolingis fairly rapid, palladiummetal shouldbe the predominantspecies.

&i Two oxides of silverare known,Ag20 and Ag 02. Ag202 is not very stableand decomposesa little above 100°C.z 5,19 Ag20 is also ratherunstable and does not become thermodynamicallyfeasible6112 until the temperatureis about 200°C, It is the oxide which is formed when the metal is heated to 200°C for a long time.13

Silver nitride,AgN3, explodes15 and is thoughtto be an aaide not preparablefrom the elementsand hence is not a possiblespecies. No stablenitride is kn0wn.S

The bromideand iodide of silverare stable17,*0,21and are defi- nitely possiblespecies? However,they are photosensitivelO,ll,13as is Ag20. It is thought,therefore, that they would be considerably decomposedby the sunlightand gamma-raysfrom the fissionproducts.

The conclusionis that the main productshould be metallicsilver with small amountsof the bromide,iodide and oxide.

Cd Cd0 is the only known oxide of cadmium, It is readilyobtained by oxidizingthe metal in airc11t13

As with zinc, cadmiumnitride is metastableSand is not thought to be a possiblespecies.

The bromide,but not the iodide is shown to be a possible speciesby the data of Brewer,17,20& but not until low temperatures are reached. There is a slightlygreater possibility of the bromide and iodidebeing formed by means of formationof the monovalent halidesat high temperatureswith subsequentdisproportionation to the divalenthalides and the metal- In any event, it is thoughtthat they will not be presentto more than two or three percentof the cadmium present.

UNCLASSIFIED______PECLASSIFIED----- B-M -_ In There are three known oxidesof indium,InO, In203 and In304.1°,17& In0 is readilyoxidized to In203 in air.lo&l In20 is the product in air oxidationat temperaturesup to 850°C.10,24 lt temperaturctsabove 850° the productis In3O4,which is analogousto Fe304.10&s24 No information on the rate of transformationfrom In304 to In203 on coolingcould be found.

The nitride,InN, is metastable8and is not consideredto be a possiblespecies.

The thermodynamicdata6t17,20,21 indicate that the bromidesand iodide8should not be presentto more than one percentof the indium.

Our conclusionis that a mixtureof In203 and In304 shouldresult with In304 predominating.

2?4 Only two oxides of tin are known, SnO and SnO;!.10,11,13SnO2 is the usual productof the oxidationin air.l0,11,13SnO bnrns when heated in air.lO9l-l SnO2 is stablebelow 1400°K.15,19

Stannrstesmay be possible,but it is thoughtthat they shouldnot be important.

Bo stablenitride of tin is known8 and, hence, it is not consideredto be a possiblespecies.

The thermodynamicdata 6 917,20,21 indicate that the bromidesand iodidesshould not be presentto'an appreciableextent. sb There ar three known stableoxides of antimo SbO3, Sb204 and Sb20$",11,13 S&O5 loses oxygen at about 4OOoC "v1 i19 to form S&O4 which in turn loses xygen at about 1000°C,l~~l~to form Sb203, which'isvery &able.38 Latimerand Hildebrandllstate the ignition productsof the elementin air to be Sk03 with some Sb204.

Antimonitesand antimonatesmay also be possible,but, as in other cases,the probabilityis thoughtto be rather small. Concen- trationconsiderations in the few known cases,the lack of knowledge concerningsome possiblecompounds, and the ease of decompositionof otherslead to this conclusion.

No stablenitride of antimony is known.8 Therefore,a nitrideis not consid.eredto be a possiblespecies.

The thermodynamicdata6,12,17,20,21 indicate that the bromides and iodidesshould not be presentto an appreciableextent.

UNCLASSIFIED__-_----__-- 24.

-----_-____-UNCLASSIFIED The conclusionis that the resultingspecies will be a mixture of 3903 and a smalleramount of Sb204*

There are three known oxidesof tellurium,TeO, TeO2 and TeOg.lO,ll& Te and TeO are easily oxidizedin air to Te02.1C9% Te03 readil:?decomposes on heatingto TeO2 and oxygen.10,13,%

The nitride,Tegl is probablyendothermic, but in any case would not be very stable.8 &i s not consideredto be a possiblespecies.

Tellmites are even less stablethan selenite& and are not expectedto an appreciableextent (cf. selenium).

The thermodynamic data 6 917~~~ indicate that the bromides and iodides should not occur to an appreciable extent.

The considerations in the case of iodine are so similar to those of bromine ,that only the differences will be mentioned here (cf. bromine).

Iodine does have one thermodynamically stable oxide, 1205, which is formed from the elements. 20 However,it is unstable above 570°K and is not considered to occur to more than one percent of the iodine present.

The iodides are even less stablethan the bromides6,12,20and the proportionexpected to occur in elemental form would be larger than with bromine.

Xenon, as with krypton, is concluded to be in the elemental state because of its lack of chemical reactivity.1°,11,24

The considerations for cesium are almost identicalwith those of rubidium (cf, rubidiumreferences). The conclusionsare also the same.

Two stable oxides of barium are known, BaO and Ba02.6~7~10~11~13 Ba20 is also known as is BaO2.13 Ba20 is doubtfuland, if it exists, is easily oxidized to BaO or to BaO2.13 Ba04 decomposes at rather low temperaturesto Ba02.13 BaO decomposes to BaO at about 700°c in air.7913 &LO is very stable 8 97 and is considered to be the most probablespecies.

Bari=\ nitride,Ba3N2, decomposes at about l27OoX.8 The thermodynamicdata 6 97 18 indicate that it should not be presentto an appreciableextent.

QNCLASSIFIED------25.

UN__ ---CLASSIFIED ----- _- The thermodynamicdata6,7,17,20,21 indicate that the bromideand iodidewould not be presentto more than one percentof the barium.

For discussionof the possibleformation of hydroxides,carbonates, and bicarbonates,see the paragraphon rubidium.

La203 is the nl knowu oxide of lanthanum.l0,11,24,37‘The thermodynamicdatag,?8,23 indicatethat the nitride,LaN, shouldnot be presentto more than one percentof the lanthanum.

Similarcalculations for the bromidesand iodides6,7,17,20,21,23 indicatethat they shouldnot-be presentto more than one percentof the lanthanum.

Ceriumhas two known oxides,Ce 0 and Ce%.7,10,24,37 The usual ignition roduct of cerium is CeOZ.1sJ4 , ,37 Ce203 is easilyoxidized to CeO2.18 924937 Hence, CeO2 is consideredto be the most probable species.

The nitride,CeN, is indicatedby the thermodynamicdata6,7@p23 not to be presentto more than one percentof the cerium.

Similarly,the data6 97 917920921923 indicate that the bromidesand iodidesshould not be presentto more than one percentof the cerium.

Two well-definedoxides of praseodymiumare known, R2O3 and RO;!.lO,%,,37 In additionto these, the most common oduct of oxidation in a;iris usuallyformulated as R&l, 10,%,3+%lthough this is possiblya solid solutionof R20 and RO2. The decompositionof R6Ol-l to R2O3 occursabove 1OOOoK.4 ,37,3S The oxide takes up 02 at room temperatureif oxidizedslightly above R2O3.fl

No data are availableon the nitride,although it is thoughtthat its stabilityshould be s i htl less than that of the ceriumnitride. If that is true, the data0 , 4, 13 indicatethat the nitrideshould not be presentto more than one percentof the praseodyminm.

.The thermodynamicdata 6 97 917,20,21 indicate that the bromidesand iodideashould not be presentto more than one percentof the Waseo- dymium. Asprey and Cunningham'sdata38 indicateRgOll as the major species.

The only known oxide of neodymiumis Nd203.7,1°,24,37

No data are availablefor the nitride,but an estimationsimilar to that made for praseodymiumindicates that the nitridewould not be presentto more than one percentof the neodymium.

UNCLASSIFIED------26.

UN NW W-W__CL~ASSIFIED B-W__ The thermodynamicaat&97917,20921 indicate that the bromidesand iodidesshould not be presentto more than one percentof the neodymium. , pm There is very little informationavailable on prometheum. How- ever9 it is thoughtthat the similarityof the rare earths13924gives a good basis for estimatingthat the productwould be Pm2O3, since the sesquioxideis the expectedspecies for neodymiumand samarium, (cf. neodymiumand samarium)the neighboringelements,

&!! Sm203 is the only known oxide of samarium. The metal is easily oxidizedin air, as are the other rare earth elements.7,10,13,%,37

No data are availablefor the,nitride,but an estimation,as with praseodymiumand neodymium,indicates it to be presentto no more than one percentof the samarium.

The thermodynamicdata 7 917920921 indicate that the bromidesand iodidesshould not be presentto more than one percentof the samarium.

Bz The only known oxide of europiumis Et~O3.~~9~39~39~4 No data are availableon the nitride,but estimationsas with the other rare earth elementsindicate that it shouldnot be presentto more than one percentof the europium.

The thermodynamicdata 7 917,2C921 indicate that the bromidesand iodidesshould not be presentto more than one percentof the europinm.

Gd The only known oxide of gadoliniumis Gd203.1°913923924 No data are availableon the nitride9but extrapolationof the estimationsmentioned in the previousmembers of the rare earth elements indicatesthat the nitrideshould not be presentto more than one percentof the gadolinium.

The thermodynamicdata 7 917920921 indicate that the bromidesand iodidesshould not be presentto more than one percentof the gado- 1initZIl.

1 There are four known oxides of uranium,UO, UOz9 U3C8 and uo .7,10911937939Th 8 usual productof ignitionin air is U3& .10,37,39 UO and UO2 are easily oxidizedin air,7923937939940 U308 decomposesto UO at about 2000°K.23940U03 decomposesto u308 between 8000 and 90009.39 From these facts,U308 is consideredto b the most probablespecies. 27.

qNCLASSIFIED------_--- The nitridesare not thoughtto be presentto more than one percent of the uraniumaccording to the thermodynamicdata.6,7,8,13

The thernlodynamicdata 6,7$&,23,39,5° indicatethat the bromides and iodidesshould not be presentto an appreciableextent.

Our conclnsion is that the most importantspecies for uranium should be U3C8 with a much smalleramount of UO3 being possible.

&2 Two oxidesof neptuniumare known,MpO2 and Mp305.37&~@,43 Mp205 is also claimed.43 Oxideshigher than MpO2 are preparedwith difficulty.37&3 MpoZ is the productof ignitionin air of the element under ordinaryco.nditions.37,~,~,43

MO data are availableon the nitrides,but by analogywrith urani&3939 no nitride is thoughtto be presentto more than one percent of the neptunium.

The data of Brewer,Bromley, Gilles and Lofgrenu indicatethat the bromideand fodide shouldnot be presentto more than one percent of the neptunknn. pn Plutoniumhas only one known stable oxide,P'~O2.3~94394594~ Pu2O3 has been prepared,but only with great diffic6Lty.a s

only one estimateof the thermodynamicdata on the nitrideis available.45 This indicatesthat the nitrideshould not be an impor- taut species.

The data availableA5& also indicatethat the bromidesand iodides shouldnot be importantspecies, Considerationsof relative concentzationsindicate that they are not possibleto any appreciable extent,

CONCLUSION

The foregoingestimates indicate that, under the temperatureand con- centrationconditions resulting from an atomic bomb detonationin air, the chemicalstates of the productsare mainly the oxides, The rare gases are, of course,uncombined, and nitrogenis largelyleft as N2; silverremains predominantlyas the metal, and the halogensexist mainly as the halides.

It should be pofited out that no considerationhas been given in the foregoingreport to the nuclearreactions which take place in the fission products. No adequatedata seem to be availableat the presenttime on the effectsof such reactionson the chemicalspecies of the radioactive

UNCLASSIFYED------.-~- II

28.

UMCLASSIF_------_ B-WIED nuclides. However,it seems very probablethat the effectwould be a very importantone.

To ill strate the point in question,let us considerthe reaction Rb890+S $9 02,) The daughteratoms are not producedin sufficientquanti- ties at high temperaturesto allow si nificantthermal decomposition of s&02. That is, the majorityof S# 4 atoms are producedby radioactive decay from Rbs9 and should occur as Sr@O2, not as Sr890,as would be esti- mated if the S@9 had been producedat high temperatures.However, this is based on the suppositionthat the nucleardisintegration does not have a large effect on the crystalstructure in which the decayingatom exists. This is not necessarilyso, for it is quite probabiethat the disintegration will have a marked effect on the structure. This problemhas not yet been fnvestigatedsufficiently for a definiteprediction of the effects.

Furthercomplications a e introducedwhen a chain of radioactivedecays is followed,e.g,, Rb97,Sr~7~JP7~2r97,Nb97~Mo97. Obviously the concentrationof a final chemicalspecies of Boo97(even without consdering the effectsof the disintegrations)would be dependenton the chemical speciesof the originaland each subsequentnucleus, the possiblereactions Involvedand their rates of reaction,and the half-livesof the disintegrations.

Hence, it is not possiblefor us to say that all of an element will occur in a predictedspecies or group of species,since part of an element presentat any time may be the result of radioactivedecay of anotheror severalother elements.

Approvedby: dJfJQ+& ScientificDirector

-_---_------UNCLASSIFIED 29.

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UNCLAS------32.

UBCLASSIFIED______

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UNCLASSIFIED_L______