The radiochemistry of iron

48 Pages·1960·1.545 MB·English

by  Julian Moyes Nielsen, U.S. Atomic Energy Commission., National Research Council (U.S.). Committee on Nuclear Science. Subcommittee on Radiochemistry

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National Research Council
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NUCLEAR SCIENCE SERIES
The Radiochemistry
of Iron
COMMITTEE ON NUCLEAR SCIENCE
L.F.CURTISS,Chairman ROBLEY D.EVANS, Vice Chairman
NationalBureauofStandards MassachusettIsnstitutoefTechnology
J.A.DeJUREN, Secveta~y
WestinghouseElectriCcorporation
C.J.BORKOWSKI J.W. IRVINE,JR.
OakRidgeNationalLaboratory MassachusettsInstituotfeTechnology
ROBERT G.COCHRAN E.D.KLEMA
TexasAgriculturaalndMechanical NorthwesternUniversity
College
W. WAYNE MEINKE
UniversitoyfMichigan
SAMUEL EPSTEIN
CaliforniIanstitutoefTechnology
J.J.NICKSON
MemorialHospitalN,ew York
U.FANO
NationalBureauofStandards ROBERT L.PLATZMAN
LaboratoirdeeChimiePhysique
HERBERT GOLDSTEIN
NuclearDevelopmentCorporatioonf D.M. VAN PATTER
America BartolResearchFoundation
LIAISON MEMBERS
PAUL C.AEBERSOLD CHARLES K.REED
AtomicEnergyCommission U.S.Air Force
J.HOWARD McMILLEN WILLIAM E.WRIGHT
NationalScienceFoundation OfficeofNavalResearch
SUBCOMMITTEE ON RADIOCHEMISTRY
W. WAYNE MEINKE, Chairman HAROLD KIRBY
UniversitoyfMichigan Mound Laboratory
GREGORY R.CHOPPIN GEORGE LEDDICOTTE
FloridaStateUniversity OakRidgeNationalLaboratory
GEORGE A.COWAN JULIAN NIELSEN
LosAlsmosScientifLiacboratory HanfordLaboratories
ARTHUR W. FAIRHALL ELLIS P.STEINBERG
~niversitoyfWashington ArgonneNationalLaboratory
JEROME HUDIS PETER C.STEVENSON
BrookhavenNationalLaboratory UniversitoyfCaliforni(aLivermore)
EARL HYDE LEO YAFFE
UniversitoyfCaliforni(aBerkeley) McGillUniversity
CONSULTANTS
NATHAN BALLOU JAMES DeVOE
Centred’Etudedel’EnergiNeucleaire UniversitoyfMichigan
Mol-Donk,Belgium WILLIAM MARLOW
NationalBureauofStandards
QmbusrRY-nADrATmNANDnADE~Y
The Radiochemistry of Iron
By J.M. NIELSEN
Hanjbrd tibO?@O?%~8
Hanybrd Aiwaic Producte Opmztion
Richland, W(ZSW
Alquglt1960
FOREWORD
The Subcommittee on Radlochemlstry Is one of a number of
subcommittees working under the Committee on Nuclear Science
within the National Academy of Sciences - National Research
council. Its members represent government, industrial, and
university laboratories In the areas of nuclear chemistry and
analytical chemistry
The Subcommittee has concerned itself with those areas of
nuclear science which tivolve the chemist, such as the oollec-
tlon and distribution of radiochemlcal procedures, the estab-
lishment of specifications for radlochemlcally pw?e reagents,
availability of cyclotron the for service irradiations, the
place of radlochemistry in the undergraduate college program,
etc.
This series of monographs has grown out of the need for
up-to-date compilations of radiochemical information and pro-
cedures. The Subcommittee has endeavored to present a series
which will be or maximum use to the working scientist and
which contains the latest available information. Each mono-
Eranh collects in one volume the Dertinent information reauired
;or-radiochemical work with an ind~vidual element or a grotipof
closely related elements,
An expert In the radiochemistry of the particular element
has written the monograph, follow- a standard format developed
by the Subcommittee. The Atomic ~ergy Commission has sponsored
the printing of the series,
The Subcommittee is confident these publications will be
useful not only to the radiochemlst but also to the researoh
worker in other fields such as physics, biochemistry or medic~e
who wishes to use radlochemical techniques to solve a specific
problem.
W. Wayne MeLnke, Chairman
Subcommittee on Radiochemistry
iii
INTRODUCTION
This volume which deals with the radlochemlstry of Iron
Is one of a series of’monographs on radiochmstry of the elements.
There is included a review of the nuclear and chemical features
of Particular interest to the radiochemlst. a discussion of D133b-
ble~s of dissolution of a sanDle and count& techniques. anti
finally, a collection of-”radi;chemicalproce&res fo; th; element
as found in the literature.
The series of monom-.aDhs will cover all elements for which
radiochemical Procedures are Dertinent. Plans include revision
of the monogra~h periodically-as new techniques and procedures
warrant. The reader is therefore encouraged to call to the
attention of the author any published or unpublished material on
the radiochemistry of iron which might be included in a revised
version of the monograph.
iv
CONTENTS
I. GeneralReviewsof the Inor@nic and Analytical
Chemistryof Iron 1
II. Reviewaof theRatiochemlstryof Iron 1
III. Tableof Isotopesof Iron 2
Iv. Reviewof Those“Featuresof Iron Chernlatryof Chief
Intiereat to Radiochemista 2
v. Dlm301utionof SpecialIronContilnlngMteriala 21
VI. CountingTechniquesfor IronNuclides 22
VII. Collectionof DetiiledRadiochemlcalProcedures
for Iron
The Radiochemistry of Iron
Rj J. hf.TCLelaen
Hanfordlaboratories
HaufordAtomicPzoducta”operation
Richland,Washington
August1960
I. GENERALREV33WSOF TEE INORGMIC ANDJUULYTICALmmlxsTRY OFIRm
“A Comprehensive!kreatlaeon Inorganicand TheoreticalChemistry”,J. W.
Mellor,Vol.XII, XIII and XJN,“Longmans,Greenand Co.,New York (1931).
“FerrousAnalysis.Modem Pnacticeand Theory”,1?.C. Pigott,2nded.
Rev.,pp. 215-231,JohnWiley and Sons,Inc.,New York (1953).
“ThechemicalElementsand TheirCompounds”,N. V. Sidgwick,Vol. II,
pp.1322-137hJUniversity-ess, Oxford (1951).
“Treatiseon InorganicChemistry”,H. Remy,Vol. II, pp252-~0, Elsevier
publishingCo., NewYork (1956).
“AnalyticalChemistry of theManhattanRcoject”,C. J. Roddenand J. C.
Warf, pp. 415-428, blcGraw-EillBook Co.,New York (1950).
“AppliedInorganicAnalysisn,Hillebrand,Lundell,Brightand Hoffman,
2nd cd.,Joh!lUiley mn&SonsP Inc.,New York .(1953).
,“ScotttsStandardMethodsof ChemicalAnalysis”,~. H. Furman,Edlter,
5th cd.,Vol. I, “Iron”,pp. h62-@’7,D+ Van Noatmnd Co., Inc.,New
York (1939).
II. REV- OF THE RADI~ TRY OF IRON
“RadioactiveIsotopesof Iron and ThetiUOe In Chemistryand Biology”,”
V. I. GoldanskliandM. B. Neiman,UspekhiKhim.Q 320.~1(1950)(In
Russian).
“Iron-60”,J. C. Roy and T. P.Kohmn, Can. J.Phya.= 649.55 (195’7).
1
111. TAB13OF 1S- ~ IRON
Method
Isotope Percent Half Iilfe Detay Energy of
Abund. (*V)
Preparation
~e52(1)
8.2 h P+(%.5@ c).8d+ Cr5°(x,2n)
X(43.5*
r @Loo* ) o.165
~e53(u 8.9 m 2.84 C#O&C,n)
2.38 Fe~(n,2n)
1.37
0.38
Fe54 5.E!&
Fe55 2.60 Y EC 0.22 Fe54(n,~)
(internal Fe*(d,p)
brems~tra- M5 (P,n)
hlung) Ii5i3(Ilpc)
Fe% 91:68
~e57 2.17
Fe58 0.31
Fe59 45.1 d @-(M@ 0.273. Fe*(n,4)
Er(54@ 0.462 Co59(nJp)
p-(o.3$) 1.560 Ni62(n@
.8 (2.8 0.191
a (57‘$ 1.*
g (43@ 1.289
~e60
-3X105 y s- CU(400Mev p)
~e61(2)
6.o m B- 2.8 Nia(n,+
‘d 0.29 N164(d#p)
Cu65(n*).
Unlessotherwiseno-d thesedata are from “Tableof Isotopes”by D.
Strominger,J. M. Hollanderand G. T. Seaborg,Reviewsof ModernPh@Qs ~
NO. 2, Part II, 628429 (1958).
Iv. REvnwoFTEosEImmJREsoFIRoN CHEKE3TRYOF
CSIEFRiTERWl TORAD1O33EMIST9
Iron iB the fourthmost abundantalementin the cruOtof the earth of
which It cormtitutes5.1 percent. It is found in practicallyall rocksand
2
q olb and Is presentin hundredsof q inerals. Becmzaeof Ita abundanceand
lt~metallurgicalpropertlea,it la the basicmaterl~lof civilizetton.Com-
poundsofh-~fundamentil Importanceto livingorganl~ma,both anluml
and vegetable,beingrequiredmainlyto promoteoxidation. Iron compounds
axe Importantcstalystsfor chemicalreactions,especiallyoxidation-reduction
reactions. Becauseof thle impor~nce and widespreadabundance,ironanalyses
are perhapsthe most commonlyperformedchemicalanaly~es,and ironseparation
prior tootheranalyeesis very important.
1. MetallicIronand the Iron Oxidesand Hydroxlde8
Iron is a whit-e,lustrous,rathersoftmetal (hardness4.5) with a
specificgravityof 7.86 and a meltingpoint of 1528°C. It exiatain two
fundamentallydifferentcrystallineforms dependingupon the teurprature.
Below9060Cand above1401°Cit f’ormea body-centeredcubiclattice. At
temperaturesbelow the Curiepoint (768°c) tion IS knownaa~-iron and la
ferromagnetic. Between9&°C and 14010Cthe latticeIs a face-centeredcubic,
non-magnetizableformknownaa ~-iron. The non-magneticbody-centeredcubic
latticeironbetween768 and 9M°C IS eometiws knownas &lron.
Imn Is generallyproducedby reductionor oxideor carbonateoreatith
carbonmonoxide. This crudeiron ia only 92-96percentpure. Steelia pro-
ducedfrom crudeIronby eliminatingthe majorproportionof the hpurltlea,
controllingtie amountof carbon, and addingalloyingmetals,especially
manganese. Pure ironcan be prepared(1)by heatingchemically~lfled iron
oxal.atein the air to form the oxidewhich ia subsequentlyreducedwith hydro-
gen; (2)by thermallydecompoalngLronpentacarbonyl;or (3) by electroQzing
aqueousq olutlonaof ferrousealte. The potentialfor the Fe-Fe(II)couple
la + 0.440 voltat 250c.
Imn dlseolveeIn hydrochloricacid,diluteadfuric acid and dilute
phosphoricacid to yieldferrousaalteof theseacide. Nitric,perchloric,
chloric,bromic and Iodicacids,althou& poaseesingdefiniteoxidizingpro-
3
pmties, alsoyieldferroussaltsif the acidsare diluteand thereaction
progsses at room temperature. With concentratedor heatedacidOferric
ealtaare formed. Hydrofluoricacid @elda slightly6olubleferrousfluoride.
Concentited nitric,iodlc and chlorlcacidsdi6aolveironvery Blowly,prob-
ablybecaueeof the foruvatlonof in601ubleoxidefilms. Ritricacidwith a.
Opeclflcglavityof 1.2 dim801ve0Ironmore rapidlythemany otherconcentra-
tionof nitricacid. Iron la not diamolvedby cold,concentratedBuMuric
acidbut doe6di6001veIn the hot acidwith the,evolutlonof auMur dioxide
to formferricsulfate. -n diesolve6rapidlyin aqueousSolutionsof Bodium
bypochloriti,ammoniumPemulfat.e, and copperammoniumchloride,
Ironform6the oxidesFeO, Fe203,Fe3~ and probablyUnstibleFe02,
Fe205 and an ironperoxideor peroxyhydrate,and tie hydroxidesFe(OH)2and
FeO(OH). Fe3~ la a doublecompound(spinel)of FeO and Fe203. Fe203has a
decompositionIxmpe=ture of 1300°Cand the otheroxidesare convertedto It
by heatingbelow thistemperaturein the pre6enceof o~gen. Ignitionof
Fe203at 1000-llOO°Cis recommendedfor analyticalpurposes. Heatingabove
lbOO°CconvertsFe203 to Fe304 and finallyto FeO by the lossof oxygen.
StronglyIgnitedFe203 dimOolveBwith dlff%cultyin hot hydrochloricacid,
beingmore readilysolublein hot 8:3 suMuric acid. The oxidesare also
readilyattackedby hydrofluorlcacid. The unignitedoxidesare solublein
hot hydrochloricacid. T&eir rate of Oolutlon my be Increasedby
addingreducingagentssuchas stannouschloride.
Ferroushydroxide,=(OH)2, is a white flocculentmaterialprecipitated
by alkalinehydroxidesfrom 6olutionsof ferroussaltsIn oxygen-freeBolu-
tion. It has a 6olubilltyproductof 3 x 10-14. In thepresenceof oxygen
(orair) the hydroxideIs slowlyoxidlzedto the ferric oxidehydrate,with
a colorchangethroughgreenand black to deep red brown. Aumoniumhydroxide
doesnot completelyprecipitateferroushydroxide,indeed,Fe(OH)2is not
precipitatedIn the presenceof a high concentrationof ammoniumsalts.
Fe(OH)2is solublein acidsand in concentratedsodiumhydroxide. The only
4