may also be c:illPd upon to give information on tlie form in which a n element exists in a composition standard as well as how much. At present very little of this type of informition is culled for in standards. I t is sufficient to knoyr and certify lion. much carbon is prescnt in a steel. As yet he generally need not certify n-hether it exists as a carbide or solid solution, although in the case of east iron the chemist attempts to certify combined and graphitic carbon. If future science and industry demand standard reference niaterisls in this area, their production will require full cooperation among metillographers, petrographers, spectroscopists, and analytical chemists. The interdependence betm-een methods of anal! sis and the development of reference standards of composition can be concluded as follows: Better methods have provided new and better standards, and proposed new standards have in turn demanded new and better methods of analysis. There is ample testimony from those who have participated in the analysis of these standards that they as analysts and their
laboratories have greatly benefited in gaining the cooperative experience in precision analysis. Out of these programs hare come the experiences that have enabled the anal!.st to do ninny tKings he could not do 50 years ago. He can now obtain tlie rare earths and hafnium in pure form and can separate niobium from tantalum in the presence of titanium. By furnishing the calibration to the spectroscopist he has made it possible, through spectrochemical standards, to speed up many processes and to introduce automation in the analytical field. But how has the analyst fared subjectively? The chances are that some metallurgist or ceramic engineer will construct a new and more complex alloy or ceramic body that will demand all the recently acquired knowledge and standards, and more in addition. Through these standard reference materials and the work connected with them he now better serves science and industry, but he finds that just about the time he has worked things out so that he can make ends meet, someone moves the ends.
LITERATURE CITED
(1) Allen, S. P., Metallurgy Division, Kational Physical Laboratory, Teddington, England, private communication. ( 2 ) American Society for Metals, “Metals Handbook,” p. 503, 1948. (3) Bright, H. A., ASAL. CHEX. 23, 1544 (1051). (4) Hague, J. L., Alachlan, L. A., Bur. Standards J . Research 62, 53 (1959). ( 5 ) James, C., J . Ana. Chsm. SOC. 33, 1332 (1911). (6) Lundell, G. C. F., Hoffman, J. I., Bur. Standards J . Research 1, 92 (1928). (7) Llichaelis, It. r., Am. Soc. Testing Illaterials Spec. Tech. Pub. 58-C (1955). (8) Michaelis, R. E., A p p l . Spectroscopy 12, 114-16 (1958). (9) Natl. Bur. Standards Circ. 552, 3rd ed. (1959). (10) Pon.el1, J. E., Department of Chemistry, Iowa State College, private communication. (11) Schoeller, W. R., “Analytical Chemistry of Tantalum and Xiobiurn,” Chapman & Hall, London, 1937. (12) U. S. Geol. Survey, Bull. 980, 7 (1951). RECEIVED for review August 25, 1959. Accepted August 25, 1959. Fisher Award
in Analytical Chemistry Address.
Recent Developments and Current Problems in Inorganic Analytical Chemistry Nuclear Materials C. J. RODDEN
U. S. Afomic Energy Commission, New
Brunswick, N. 1.
The analysis of nuclear materials is divided into major and minor constituents. Under major constituents the analysis of nuclear materials used as fuels are uranium, thorium, plutonium, and alloys of these elements with other metals. The problems involved in the chemical analysis of these materials are considered as well as those involved in the determination of the isotopic composition of uranium, which is at present the most important nuclear fuel. The determination of minor impurities in fuels as well as in moderators i s considered under two categories. The most important is that group of elements which is undesirable because of neutron absorption. The other group is elements which are undesirable because of the effect on the metallurgy of the nuclear fuel or the moderator.
I
almost 20 years since I had the pleasure of addressing the
T HAS BEEN
1940
ANALYTICAL CHEMISTRY
American Chemical Society in Boston. Many old-timers will recall it as the year of Swampscott. At about the same time, contacts were first made with the Government on a matter which later evolved into the hlanhattan Project. This project was responsible for the work on uranium and plutonium that led to the present world-wide interest in nuclear energy. Since the beginning of, the project, the analysis of materials has been of prime importance. At present, the expansion has been such that a considerable proportion of the analysts in the United States have some interest in the control of raw materials, plant processes, products, and other allied subjects related to the nuclear-energy field. The field is large. I would like to consider the analysis of nuclear fuels which are used in power reactors. The data given in Table I (28) summarize the various types of reactors at present in use: nearly 150 p o w r and
research reactors, as well -3 another 50 or so devoted to plutonium production and ship propulsion, among other things. When we look over this array, we can see that uranium, plutonium, thorium, beryllium, carbon, or graphite, and their compounds, along with heavy water, are the materials in which interest centers. At the present time, uranium is the fuel in largest use. For reactors using normal uranium, the absence of neutron absorbers is desirable. Fuels highly enriched in uranium-235 may contain intentional additions of a neutron absorber such as boron, which can act as a burnable poison. Problems in the analysis of graphite and heavy water have essentially been solved. Interest a t present is in analytical p r o b lems associated with uranium, thorium, plutonium, and beryllium. METHODS FOR OBTAINING’SOLUTIONS
I n the analysis of alloys, the first problem frequently encountered is dis-
solving the niateridl. Table I1 is prepared from a reccnt report ( I S ) , and summarizes the reaction of some solvents u i t h metallic uranium and its alloys. The possible use of ceramics as fuel rods raises additional problems. The published literature on this type of materinl is merger, but the preparation of solutions of sintered oxides of uranium and beryllium (54) is illustrative. The uranium dioxide is partially dissolved in hot nitric acid. The beryllium oxide skeleton resulting from this treatment is dissolved in refluxing sulfuric acid, and finally, any insoluble residue is fused with sodiuiii perouide. As another example, uranium dioxide-aluminum oxide fuel elements Ere fused n i t h potassium pyrosulfate prior to an x-ray spectrometric analysis (26). The thorium oxide-uranium oxide fuel elements will present a more formidable problem, METHODS OF SEPARATION
Some methods which have been used for the analysis of certain alloys of uranium are listed in Table 111. Khile not complete, the table illustrates various techniques used to obtain solution of the alloys, and t o separate and determine the uranium. I n the volumetric determination of uranium, certain elenients which do not reduce or oxidize may be ignored. One method most often used to remove interfering elements is the extraction of the cupferrates with chloroform from a solution containing 10% of sulfuric acid. This stparntion will remove tit:miuni, vnn:idiuni, niobium, molybdc num, and iron, us n.c.11 :s a number of other elenic,nts. A s can be seen, the elcnients that most seriously interfere with an osid:?tion-reduction procedure :'re rcmorcd. ;Inotliw separation frequmtly used is the ethcr extraction of the nitrate, used by our award recipient in the pre-Manhattan project days for the preparlition of high-purity uranium salts. Tributyl phosphate is frequently used in the extraction separations. Other separations niay be required for a particular combinat'ion of elements.
Country USSR UK France
USSR
France Italy USSR US Czech US USSR US US US
Table I. Types of Reactors Now in World-Wide Fuel Jacket Metals G (57;)s Stainless steel hlg-alloy U U AIg-Zr Al-alloy U u llg-alloy u 11y-alloy U (1.3%) Stainless steel u (2.3:;) Staiiiless steel U Be-llg U (1.8f2) A1 Pu 1
G-Zr (90%) u-Alloy (2"?c) u-Mo ( 2 7 5 4 )
UI< US
us USSR us us
Germany USSR
us us
Alloys Zircaloy-3 Stainless steel zr-c238-~0-a110~stainless steeiblanket Compounds Be Zi r ca 1oy -2 Stainless steel Zr-Nb Stainless steel Zircaloy-2 Zircaloy-2 Zr 1
Al-Alloy Italy Zr Sweden Zircaloy-2 Per cent values indicate enrichment of UZ36
Use
Iiotlcrator Graphite Graphite Graphite Gra1)liitc tirx1)Iiite Grapliite Graphite Grapliitc Heavy H 2 0
Organic tcrpheii Fast HJO H ~ Z VII?O Y Fant
Graphite He0 HZ0 HZ0 H20 HzO H2O
Hz0 Hz0 Hz0 €120
Heavy HzO
(1
Table II. Solution of Uranium and Its Alloys Reaction HXOs Common solvent. In the case of Zr and S b alloys can form an explosive residue ( f 9). Agitation, or may be spontaneous. Kith 17, Zr, violent explosions have occurred. Adding HF prevents this HC1 Reacts rapidly but forms black precipitate. \lay bc hydrated U(II1)-(IV) oxide. XaClOo, H202, Br react rapidly Aqua Regia Good for Pt metal alloys. If Zr prrsent, desirable to add H F HClOa When hot, 707, HC10, reacts rapidly and spcctacv1:irly. \lay actually cause sparks. Lower concentration of HC10, has no effect Unalloyed U does not react. If H,O, is added, metal is attacked HzSOd slowly. Anodic solution is satisfactory HF Generally not used alone Br in ethyl acetate Reacts rapidly with U and Zr HC1 in ethyl acetate Reacts a t a moderate rate. Dissolves completely, unlike HC in HzO NaOH, H ~ O Z Reacts moderately
Solvent
URANIUM
Fortunately or unfortunately, depending on the point of view, uranium evists in several valence states. Those of interest to the analytical chemist are uranium(III), urnnium(IT'), and uranium(V1). Oning to the relatively low oxidation potcntial of the uraniuni(V1) -uranium(IV) couple, the element can be quantitatively converted to either valence state at will. Because uranium(II1) is a pon erful reductant, exposure to the air for a few minutes oxidizes it to the quadrivalent form, The uranium(1V) is then titrated by a n oxidizing agent to uranium(T'1). The reducing ?gents used a t the pres-
ent time are zinc amalgam and the lead reductor. The zinc reductor has thf disadvantage that some uranium is reduced to the trivalent form, which must be oxidized to uranium(1V). It has the advantage that sulfuric acid solutions can be used. The lead reductor method (9)is usually used in 1N hydrochloric acid. It is principally used for the analysis of low-grade ores, but has been used in England (3) for the analysis of high-grade uranium products. Other studies (38) indicate its application to high concentrations of uranium. The method has the advantage that uranium(1V) appears to be formed exclu-
sively, and the disndvnnt:gc that sulfuric acid must be :tbsont. The dircct titration of uranium(1V) u ith dichromate is sluggish a t room temperature; a ferric salt and phosphoric acid are usually addtd to form ferrous ions, Rhich react nith dichromate a t a satisfactory rate. Sodium diphenylamine sulfonate is usually usFd as an indicator. I n the ceric sulfatc titration, phosphoric acid is usrd t o speed the oxidation. Ferric iron may nlso be used, and o-phenanthroline (furoin) is usrd as an indicator. Standardization is generally made against a n amount of U308, such as the NBS Standard UaOs 950, VOL. 31, NO. 12, DECEMBER 1959
0
1941
Table Ill.
Alloy U-Ta U-Nb U-Stainless U-A1 UOn-Al?Or
U-Th U-Bi
U-Ti U-Zr
U-110
Methods Used for Certain Alloys of Uranium
Solvent H2SOI HSO8-HF-HzSOI HCI-HNO3 HCI HCI Fusion liB.0, Solution in H2SOl HCI-HCIOr HXOJ-HF HSO,
Separation Sone Cnpferron-CHCb. Hg-Electrolysis Sone Xone Sone
Determination Differentialspectrophotometry (a) NH4 diuranste ( 8 8 ) Jones reductar-KLhOi (80) Ph-reductor-ceric sulfate ( I Jones reductor-ceric sulfate ( 4 ) X-ray spect.rometry (86)
Sane
Zn-amalgam-ceric sulfate ( 1 4 )
Volatilization of Bi as bromide U on Ih.4cidite FF Resin HClelution HS01-H2SOI-HF Cupferron-CHCla extraction HS03-HF-H2S01 Ciipferron-CHC& extraction HS03-H1ROI sone
equivalent to the uranium content of the sample. Precisions t o ahont 1 part per thousand are obtained. A more precise determination of uranium is required in certain cases involving high-puritymaterials. I n one of the more precise methods (39):the uranium is reduced in the Jones reductar! and the nranium(II1) formed is oxidized to uranium(1V) ivith either dichromate or air. The reaction is follolx-ed potentioniet,rically with the platinum-tungsten electrode system. The resulting uranium(1V) is titratrd potentiomctrieally with KBS Standard K&Or using the same electrode system. By using a slightly deficient wighed amount of the solid salt, and finishing the titration with a dilute (0.005 t o 0.01S) clichromate solution, a standard deviation of 0.00.51~o was obtained. An alternative procedure ( 1 7 ) reduces the uranium by electrolysis with a mercury amalgam electrode. The. nranium(I11) is oxidized by air and tlie reaction is followed potcntiometricaily. A slight excess of solid dichromate is added, and the exw s s dichromate determined potcntiometrically with ferrous sulfate using the gold-calomel clcctrode system. A standard deviation of 0.0032% iT-as obtained. Other methods for the determination of uranium as a major constit.uent hare lieen proposed. Differential colorimetry in both sulfuric and phosphoric acid ( I , 6 , 3 7 ) media has been nscd. The absorbance of the solution is measured against that of a solotion of known uranium concentration at a wave length of 420 t o 430 mp. Temperature control may be necessary (1). Gravimetric methods for the determination of uranium.are in use, especially abroad, and the final product which is weighed is generally considered t o be USOS. The ignition temperature required t o form this compound stoichiometrically is
1942
ANALYTICAL CHEMISTRY
Pb reductor (83)
Tannin-Ua08( 8 4 ) Tannin-UIOs (855) Ph reductor-ceric sulfxbe (1.5) Differmiid sprctrophotomet.r? ( 8 )
still undetermincd, though temperatures of 850" to 1100" C. have been used. It appears to depend to some extent on the previous history and type of compound ignited, and is temperaturcdependent. Our own csperiencc iudicates that 1100" C. is too high if tlie usual procedure of ignition in a muffle and cooling in a clrsiccator is usrd. A range of 850" to 0.50" C.. appi'ars to be more satisfactory. X-ray fluorrsccnt nlrthods have been nsrd (Be), with strontium as an iiitcrnal staiidard. One of thc prohlcms remaining is tha determinatioii of uranium in faliricatcd furl elcnic.nts. Various ~nctliods,such as M a y absorption, b r a y sprctrometry, x-ray absorption and fluorcsernrr, and thermal neutron tranrniission (13), hare lwen suggested. In rccmt years thc isotopic analysis
Figure 1.
of uranium has been of eonsiderahle importance. The most precise method in routine operation is one in which the gaseous uranium hexafluoride is analyzed in a mass spectrometer. Thc "memory cffeet" is bad in this type of instrument. The surface-emission mass spectrometer has been used in recent years. While, at present, the precision is not as good as it is with an instrnment in Tvhich gas is used, the surface-emission method has the advantage that t h r memory effect is slight. This allom the use of one instrument for a variety of isotopic compositions. Because of the cost of mass spectrometric analysis, interest has increased in methods (27) such as (1) emission spectroscopy, using both a photographic plate and a multiplier phototube devicr (presence of rarying amounts of uranium-236 in a enrrcnt material is a problem in this type of analysis), (2) ncut,ron activation analysis, both direct and hy scparatioii of fission products, (3) fission counting, (4) alpha pulse-height analysis, and (5) y-ray spectrometry. The estimated costs for the equipment used for the various types of isot,opic analysis are given in Table IV. As can I)(, srcn, costmise the y-ray sprctroiiirtrj- mcthod indicates promise. As priwnt the prrcision is far from that of thc mass sprctroiuetric method, hcing of thr orrlrr of 0.5 to 1.5%. All methods in us,! at the present tinic usnally arc (lrpcmlent on standards issurd by the Satioiial Jhrean of Stanrlarlls. PLUTONIUM
Anotlrrr impqrtaiit elrnicnt which 110 doubt, will in t,lie future increase in use is plutoninm, possibly as a plntoniumnranium shy.
Laboratory for handling plutonium materials
. ,.
Tlie health hazard due to alplia radiation involved in the handling of plutonium materials requirm rather claborate enclosed box systems. Figure 1 shows our laboratory for this work. This adds to the problems of the chemist, but the equipment is not of the same coiiiplevity as used in highly radioactive material. Plutonium is a chemically reactive material which in a finely divided state is pyrophoric. The metal melts a t about 630" C., and is readily soluble in hydrochloric, hydrobromic, hydrofluoric, 72% perchloric, and S5Yc phosphoric acids. Moderately concentrated sulfuric acid dissolves the metal slowly but, d i k e uranium. nitric acid is without action. K a t e r rraets wit'li the metal slon.l~-. Alkali hydroxidw (lo not attack it. The common ositlc, PuO?, is vcrj- difficultly soluble.. 111 many instances solution in nitric acid with a small amount of hydrofluoric acid \Till suffice, but in other iiistaiicrs fusion with pjmsulfate is noccssary. In some instances this is riot satisfactory. Separation of plutonium ma>- 1)c accomplished by precipitation as pcroxide, tetraiodate, tetrahydroside, diosalate, or trifluoride. Ion exchange methods have: bt3en used (21) for thc *cparation of plutonium by absorbing plutoniuni(TI) on Dowes and eluting with hj-ciroxylamine and 1-11 nitric acnitl. Rr.cover- is about S9.9yc. Solvent extraction lias 1)c~windicated :IS a satisfactorj- method for sqxirating plutoniuni. Table \- iiidicatw the recover>- with various solvc,iite ( 2 1 ) . 'I'hc,iioyltrifluoro~ict,toiie (TT.1) i n benzme is a n excellent, solvent for plutoiiiunii IV) in nitric ac,itl. a i ~ l~ctlfor plutoiiiuni is reduction t,o plut~oiiiiitii(II1) with zinc nnialgaiii or in a ,Jones rcductor follon-td by titration to plutoiiiuni(1T) with crrir sulfate using 3 1)oteiitioiiietric end point. -Is can be swii. t,Iiorc is hiit onv valence change. Rcwntly Netz and coworkers a t Los .Ilntuoe osidizcd thc plutonium to plutoiiiuni(T1) with fuining perchloric acid, thclii atldetl ferrous sulfate in excess to form plutonium(IV) and titrntcd tht, PSCTSS nit11 ceric sulfate to a potcntioiiic,tric end point. This result,s iii a t\vc: valence change. By using samples of about 0.4 gram instead of the fornierly c,mployed riiilligrani samplrs, the precision is increased to about 0.037,. Coulonietric determination with electrolytically generated ferrous ion has ticen used for micro amounts (8). Differential speet~~op1iotoiiict~~(29) has been applied to the determination of plutonium in a liydrochloric acid solution with a precision to 0.057,. The sample is dissolyed in 1 N hydrochloric acid and hydroxylamine hjdrochloride is added to form plut,onium(III). RIeasurenients are made a t 6650 -4,
30
Figure 2. Absorption spectra of plutonium(lll), (IV), and chloric (VI in 0.5M acid and hydroplutoniurn(V1) in 0.5M nitric acid
20
E
c -
5 4 \0f :upk& j/
3o
0, 0 c u
z I-
J
o
I
20 IO
n 20
1
PUlYI
i
50 40
30
20 IO
0
400
300
630
700
eo0
WAVE LENGTH
goo
1,000
1,200
mp
The absorption sprctra of plutoniuin(III),plutoniuni(IT'), aiitl plutonium(Vj in 0.531 Iiytlrochloric acid are given in Figure 2 . The plutonium(V1) is in 0.5M nitric acid ( 2 1 ) . X-ray spectrometric nictliotls h a w been usctl for the detcrminntion of plutonium (12). I n sonic inst'ances no scparatione a w l i t sorption ni(tho(1s h : i v ~ also h ~ ~ cni-n ploycd. Thorium is iiiiotlirr possihlc~mct:il to be u s t ~ liii rcbuctors. The chcniistry of' thoriuni is such that crswti:tlly 0111). gravimetric nivtliotls itre usctl, althougli titration with (ctliylenc~diiiitri1o)tctraacetic acid h : ~lwcm ciiiployc~i ( 1 4 ) . Fon nrw nicdiotls 1 i : i ~I m ~ n drvc~lopeti for thorium. Ber>.lliutii. n ' l i i k not i i i i u c h r f u r i is usrtl as a iiicitl(>rator. l'hc roninirrcial bcrJ-lliuni of (wriitiierc(' contains niany inipuritic,i, ;iiirl separations are iiccessary bcfort~d(%cwniiiiiig the beryllium as oxide. Thv usual nirthotl is to rvm o w aluniiiiuiii. iron, et'c.. by osiiie and then to prccipitato the. herylliuin as hydroxide,. Tlic prwipit:ttc is charretl, and ignitvtl first at 600" C. and finally to 1100" C. Yolatilization of I k O can occur in the prrsriicc of water. The US? of (ethylcnedinitri1o)tetraacctic acid to complex intcrfering elenients allows beryllium to be precipitated directly (6). This method has liern applied to the analysis of berj-Ilium metal. The impurities in uranium, plutonium, and bt~rylliuniare determined by spectrographic analysis of the oxides, n-ith the exccption of certain nonmetallic elemcnte. Tlie carrier-distillation technique (35) developed a t the Satioiial Bureau of Staiidards in 1941 is applicable to tlic a h o w clcnicnts.
Table V. Behavior of Plutonium toward Some Organic Solvents f~Illl(lltl0ll. to11 SH,SO, I I! I150 )
VOL. 31,
NO. 1 2 , DECEMBER 1 9 5 9
1943
Table VI.
Element
3 As Au B Ba Be Bi Ca
A 0.05 5 5 0.3 0.1 10 0.1 0.5
...
Spectrographic Limits
Parts per Million B C
E
. . . . . .
...
. . . . . .
...
. . . . . .
. . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 2 ... ... 3
... ...
... ... ...
...
...
...
Element Gd Ge Hf Hg Ho In Ir K La Li
of Detection for Impurities in Uranium and Its Compounds A
...
0.5
*.. 10
...
0.5
2 .
...
A. B. C. D.
8 0.3 ...
... ...
1
...
. . . . . . . . . . . .
. . . . . . . . . . . . ...
. . . .
. . . .
1
. . . .
...
...
0.04 0.04 0.02
... ...
Na Nd Ni P Pb Pd
Carrier-distillation concentration method on oxide Direct examination of the oxide Examination of refractory concentrate in BilOa Examination of Pt metal concentrate in Au
hydrochloric acid and then further impurities are eluted with 0.1N and 0.05N acid. The impurities are determined spectrographically, by the copper spark technique. The method, while applicable to uranium, has more promise in the analysis of plutonium, as i t avoids burning a large sample of 100 mg. of PuOz with the containing problem always requiring consideration for health reasons. A cupferron extraction followed by a copper spark analysis is also used in conjunction with the carrier-distillation techniquc for plutonium ( 2 1 ) . The follon ing carrier-distillation technique, used for uranium, is applicable to other elements. Essentially the method consists in igniting the compound or metal t o U308, mixing the oxide with gallium oxide, and then using a direct current arc for the exposure. Concentrations can be obtained by use of the photographic-plate method or a n instrument equipped n ith photosensitive tubes. With certain refractory elements, the sensitivity obtainable by means of the carrierdistillation technique is not sufficient and a cupferron extraction from 10% sulfuric acid is used to Concentrate the element in question. An ion exchange procedure for concentrating tungsten, tantalum, and niobium has been used. A nitric acid solution is passed through a Dowex 1-X8 resin column. The resin is then ignited. The rare-earth elements and metals of the platinum group must also be concentrated. The limits of detection obtainable a t our laboratory are given in Table VI. Obviously spectrographic determinations are, in the long run, dependent on chemical analyses.
1944
0
ANALYTICAL CHEMISTRY
..*
... 10 ... ,.. ... ...
... I
.
.
0.5
... ... ...
2 0.5
(ij ...
0.1
... 1
cs CU DY Er EU Fe Ga
Parts per Million C D
E
...
0.04
...
...
... . . I
... ...
...
... 0.04
...
...
100
...
...
...
0.1
. . I
. . I
... ...
..*
0.5
...
...
...
... ... ...
Element Pr Pt Rb Rh Ru Sb sc Si Sm Sn Ta Tb Th Ti T1
A
Parts per Million C D E
. . . . . . . . .
0.5
. . . . . . . . . . . .
0.1
. . . . . . 1 1 . . . . . . . . . . . 20 . . . . . . 5 10 ? . . ...
..
3
... 1
... , . .
... ..
3
...
40
...
..
3 ...
... *.. ... *.. ...
...
0.3
...
...
1.o 1
...
...
. _
Zn 20 . . . . . . ... Zr ... 1 ... ... E. Examination of concentrate of rare earth oxides ( ). Determinations not usually made in the general scheme by the method involved
Table VII. Methods in General Use for Determination of Nonmetallic Impurities in Uranium
Oxygen in beryllium, until recent years, was determined by distillation of the beryllium as chloride or bromide, followed by a colorimetric determination of the B e 0 remaining. Recently a method employing methanol-hydrochloric acid solution of the beryllium leaving the B e 0 undissolved has been developed for vacuum cast beryllium
Component DeterMethod mined Sample U metal 1. Volumetric after C combustion 2. Capillary trap 3. Low pressure methods U metal 1 . Kjeldahl x 0 U metal 1. Vacuum fusion, Fe or Pt bath 2. Fusion in argon atmosphere U metal 1. Vacuum fusion H 2. Vacuum extraction
The argon method has been applied to the determination of oxygen in beryllium metal, using a nickel bath (16).
I n some instances chemical methods are used-essentia!ly those used for many other materials adapted to the elements in question. For example, boron is usually done colorimetrically n-ith curcumin, iron with o-phenanthro line, etc. These procedures have been adequately described (11,SO-SS). The methods of analysis for nonmetallic impurities are indicated in Table VII. The vacuum fusion method has not been found generally applicable to the determination of oxygen in beryllium. I n recent years the vacuum fusion method has been displaced in many instances by the methods of Smiley ( S 6 ) , whereby the carbon monoxide formed is swept out in a current of argon and converted to carbon dioxide. Various methods of determining the carbon dioxide are used, such as those invohing conductivity methods or capillary traps.
(5) Banks, C.V., Burke, K. E., O’Laughlin, J. W.,Thompson, J. -4., A\AL. CHEM.29, 995-8 (1957). (6) Brewer, P. I., Analyst 77, 539-41 (1952). (7) Brody, J. K., Faris, J. P., Buchanan, R. F , ANAL.CHEX.30,1909-12 (1958). (8) Carson, W. N., Jr., T’anderwater, J. W , Gile, H. S.,Ibid., 29, 1117-22
(10).
LITERATURE CITED
(1) Bacon, A., Milner, G. W. C., Analyst 81, 456 (1956). (2) Bacon, A , , hlilner, G. W. C., Atomic Enerev Research Estab. ( G . Brit.). “Apgications of Differential Spectro: photometry to the Determination of Uranium in Various Binary and Ternary Uranium Base .411oys,” AERE-C/R1749 (September 1955). (3) Ibzd., “Volumetric Determination of Uranium in Aluminum-Cranium Alloys,” AERE-C/R-1813 (>larch 1056). (4) Banks, C. V., Iowa State University, “Analysis of Certain Uranium Alloys,” M-3056.
(19.57).
(9j-Cioke, W. D., Hazel, F., hIcKabb, W. M., I b i d . , 22, 654 (1950). (10) Eberle, A. R., Lerner, A i . W., Metallurgia 59, 49-52 (1959). (11) “Fir& Conference. on Analytical Chemistry in Nuclear Reactor Technology, Xovember 4-6, 1957, Gatlinburg, Tenn.,” U. S. Atomic Energy Comm., TID-7555 (August 1958).
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