---

.,

-.

.-

National Academy of Sciences National B NUCLEAR SCIENCE Research Council

v
SERIES

The

Radiochemistry

of Antimony

COMMITTEE
L. F. CURTISS, Chainnmt National ureau of Standards B

ON

NUCLEAR
ROBLEY

SCIENCE ,;
D. EVANS,

ViceChakan

Mamachueetts

Institute of Techndw .,

J. A. DsJUREN, Secretary We8ttnghouse Electric Corporation C. J. BORKOWSIU Oak Ridge National ROBERT College SAMUEL EPSTEIN California hmtituta of Technology U. FANO National Bureau HERBERT Nuclear America J. W. IRVINE, Laboratory Massachusetts E. D. KLEMA Northwestern .. . W. WAYNE University of Unlverstty .. . MELNKE JR. Institute of Technology

G. COCHRAN and Mechanical

Texas Agricultural

Michigan

J. J. NICKSON Memorial Hospital, New York

of Standards

GOLDSTEIN Corporation of

ROBERT L. PLATZMAN Laboratoire de Cblmie Physique D.

Development

M. VAN PATTER
Researoh Foundation

Bartol

LIAISON
PAuL C. AEBERSOLD Atomic Energy Commlsslon J. HOWARD McMILLEN National Solenoe Foundation

MEMBERS
CHARLES K. REED U. S. Air Force WJLI@M E. WRIGHT J3ffice of Naval Rssearoh )

SUBCOMMITTEE
W. WAYNE Untverslty GREOORY Florida GEORGE MEINKE, of Michigan R. CHOPPIN Chainnun

ON

RADIOCHEMISTRY
HAROLD fURBY Mowd Lalmatory GEORGE LEDDICOTTE

State Univemity A. COWAN Sotenttflc Laboratory

Oak Ridge National Laboratory JUTIAN NIELSEN

Los Alemos

Hanford Laboratories ELLIS P. STEINBERG Argonne National Lsborato~ PETER C. STEVENSON of CaUfornia (Llvermore)

ARTHUR W. FAIRHALL ~niverslty of Waabingtcm JEROME HUDIS Brookhaven National Laboratory EARL HYDE Unlverslty of California

Univerai@

(Be*eley)

LEO YAFFE McGill Universl@

CONSULTANTS
NATHAN BALLOU Naval Radiological Defense Laboratory JAMES DeVOE University of Michigan

WILLIAM MARLOW Nwional Bureau of Standards

CHEMISTRY

The Radiochemistry

of Antimony

WILLIAM
Phillips Atomic

J. MAECK
Petroleum Energy Idahu Company

Division

Idaho Falls,

February 1961

Subcommittee on Radiochemistry National Academy of Sciences National Research Council

Printed in USA. Price $0.50. Avnilnble from the Office of Techuicnl Services, Dcpertment of Commerce, Washington 26, D. C.

FOREWORD

The Subcommittee on Radlochemistry 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 chemlst~.

The Subcommittee has concerned Itself with those areas of nuclear science which tivolve the chemist, such as the collection and distribution of radiochemlcal rmocedures. the establishment of specifications for radloche~lcally pu;e reagents, availability of cyclotron time for service Lrradlatlons, 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 radlochemlcal information and,procedures. The SubcomniLttee has endeavored to present a series which will be of maximum use to the worktig scientist and which contatis the latest available information. Each monograph collects In one volume the pertinent information required for radlochemlcal work with an tidlvldual element or a group of closely related elements.

An expert In the radiochemistry of the particular element has written the monograph, following a standard format developed by the Subcommittee. The Atomic Energy Commlsslon has sponsored the prtitlng of the series.

The Subcomml.ttee Is confident these publications will be useful not only to the radiochemlst but also to the research worker In other fields such as physics, biochemistry or medicine who wishes to use radlochemlcal techniques to solve a specific problem.

W. Wayne Melnke, Chairman Subcommittee on Radlochemlstry

iii

INTRODUCTION
ThlB volume which deala with the radiochemistry of antimony is one of a serl.es of monographs on radlochemistry There 16 included a review of the nuclear of the elements. and chemical features of particular Interest to.the radlochemiet, a discussion of problems of dissolution of a sample and counting techniques, and finally, a collection of radlochemlcal procedures for the element as found in the literature.

The se~les of monographs will cover all elements for Plans include which radiochemlcal procedures are pertinent. revision of the monograph 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 antimony which might be included in a revised version of the monograph.

ACKNOWLEDGMENTS
The author wishes to express his appreciation to James E. Rein for reviewing the manuscript and to Deanna Shawneen Anderson for typing and preparing the manuscript for publication.

iv

CONTENTS
I. General Review of the InorgarJIc CheldEtmy of Antilumy . . . . . General mklleof Reviews Alltinuny of the ~ochemistry . . . . d . . . _ical . . of . .

. . .

. . .

. . .

. . .

1 2
3 9 9 9. 10 10 U u

II. III.

Antimony . . . .

IeotcrpeE.

Iv. General Chmiatly of Antimony . . . . . . . . ...*..

1.

Oxidation States . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . .

2. Ebmnantal ktdnkmy.... . . . 3._e80f 4.

5.

Autimmy.. ... . kmmmy.... . . .

~mie .......

Eydri&of
Boluble

6. 7.
8.

Insoluble Caqounda . . . . . . . . . . . . . . . .. volatile CcmpoUdB end Distillation of Antimony . . .

Cauplex Isotopic Ioneami Exchange Chelates Reactiona Antimny . . . . . . . . . ad . . . . . . . . . . . . .

14 14 15

9.
V.

Hot-Atom

Chmnietry to Separations

Analytical Yield

Chemistry of De-terminationa Elrtraction

. .

Applicable . . . . . . . . . . .

. . . . . . . .

16 16 16 19 20 m 21 22

1.

Eolvent ~. 1 1.2

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Ion-Ae80ciation Chelate Sywtmne

Syatema, . . . . . . .

. . .

2.

Clm3mat43gTl%phyof 2.1 2.2 Ion-Exchange Inorganic

Antinlomg . . . .

Alumina

hC~=E1.

2.3

Paper Ch-onrttqnsphy . . . . . . . . . . . . . .

3.

Distillation

and Volatlllzation

4.

Electrochemistryof Antinmny . . . . . . . . . . . . 4.1 Electrodepositlon . . . . . . . . . . . . . . . 1+.2 Polarography . . . . . . . . . . . . . . . . . .

4.3kllalgmls . . . . . . . . . . . . . . . . . . . .

23 23 24 25 25 25 26 27 28 28 48

5.

Gravimetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. ..0

6.@ectrophotometry 7. VI. VII.

!l?itrlmet r y . . . . . . . . . . . . . . . . . . .

Dissolutionof Antimony ContainingCompounds . . . . . . Counting lkchnlque s.... . . . . . . . . . . . . . . . . . .

VIII. CollectedRadiochemice.1ocedures for Anthony W

IX. Neutron ActivationAnalysis . . . . . . . . . . . . . .

vi

The Radiochemistry of Antimony

WILLT.AM
Phillips Atomic

J. MAECK
Company Division Idaho

Petroleum Energy

Idaho Falls,

I.

GENERAL REVT.EWS THE INORGANIC AND OF ANAUITCAL -STRY OF ANT9110NY

1.

EKllebrti; W. F., Lundell, G. E. F,, Bright, H. A., Hoffman, J. I., Applied InorgauicAnalysis, 2nd EH., Wiley, New York (1953). Sidgwick,N. V., I!he Chemical Elements and Theti Compounds,Oxford Rress, Iondon (1950). ion of Traces of Metals, Sandell, E. B., CalorimetricDetermdnat 3rd E&., Interscience,New York (1959).

2.

3.

4. Welcher, l?.J. organicAnalytical ReagentE, D. Van Nostrmd, New York (lg48~. 5. Kolthoff, I. M., Belcher, R. VolumetricAnalysis,Vol. III, Interscience,New York (1957\. 6. Wagner, W., Hull, C. J., Markle, G. E., AdvancedAnalytical Cheudstry, Reinhold, New York (1956). Lamdell, G. E. F., Hoffman, J. 1., Out Unes of MethodB of Chemical Analysis,Wiley, New York (1951). Analytical Chemistry, Wibon, C. L., Wilson, D. W., Comprehensive Vol. U, ClassicalAnalysis, Elsevier Publishing,Amsterdam (1959).
Analysis, 5th Ed., Vol.

7. 8.

9.

Scott, W. W. (N. H. Furman, 13i., Standti Methods of chWOiCd ) 1, D. Vsa Nostrand, New York (1939).

ical Chemistry of the Manhattan Project,McGraw10. Rodden, C. J., Hill, New York (1950 . T 11. McAlpine, R. K., Soule, B. A., Prescottand Johnson Qualitative Chemical Analysis, D. Van N06trand, New York (1933).

12.

Morrison, G. H., FYeiser, H., SolventExtraction in Analytical chemistry,Wiley, New York (1957).

II. GENERAL REVZEWS OF THE RADI~STRY 1.

OF ANTIMONY

Coryell, C. D., Sugsrmsn,N., eds. RadlochemicalSttiios: The Fission Prcducts,hok 3, National Nucleex Euergy Series, McGrawHill, New York (1951), Finston, H. L., Miakel, I., Ann. Rev. Nucl.
&i., j, *g-*

2.

(1955).

III. TABLE OF ARITMONY ISOIUPES

IBot ope

HaJfLife 60m -/
15 m

Type of Decay
0.75,

Energy of Rad.iat h Mev ion

l.lo

Assignment ma6s assignment uncertain In

~u6

0.060, 0.09)
1.5, 2.4

(Z6-Mev a, 3n) ? ~5-Mev p, n) (C4 m) ~ ~ ?

0.90, 1.31, 2.22 60m w

2.8 h

b+
v

1.45
0.41, 0.6 0.95,

~n115 1.31 InU3 ~n115

SnU6

(SMev a . n) (a, 2u) ?

(>Mev

p+ (2.5$) EC (97.5*)
.

d,n) 7

0.161

Sn7
InU5

(5-Mw p,n) ?
(11-Mev

3.5 m

IT (7)

a,n)

? ?

B+
-Y

3.10

h115

(16-k!ev a,n)

1.2b InU5 Sn7 O.0~, 0.255, 1.03, 1.22 (ZQ-Mev a,n)? (10-Mevd,n) ?

5.1 h

No p+ &=o.q) EC Y

III. TABIE OF ANTIMONYISOTOPES- cent d

Isotope

Half-1ife 38.0 h

Type Of Decay EC
7

Ehrgy of Radiationin Mev

0.53 bremstrahlungendpoint

Assignment
~ ~6h g#9 snug (5-Mev p,n)

0.024

+8 5.8 d No IT No ~+ .
16.4 m 0.09, 1.70 1.18 0.203, 1.040, 1.170

(10-Mw d,n) 7 (18-M= d,n) (l&Mev d,2n) (<50-M~ ~ n) ,?

sn~9 SnH ~1~ Sbla snug SbW

!s+
7

(17-Meva,n) ? (5-Mevd,n) ? (15-Mev. n,2n) ?

z2.zz3.5 m

IT v
0.061, 0.565 0.74, 0.93, 1.40, 1.97 0.075

#21

(th n, ~ )

2.@3 d

!9+(0.01$) P-(9fi)

Sb121 (th n, 7 ) Sn122 (5-Mevd,2n) 7

EC(9)

OF ISOTOPES- centd III. TABIJl ANlLQ40NY

!&pe Isotope Half-Llf e 42.75$ ZLm IT Y p- (w) .#2h ml

1.3 m o.olt35 ~ 2.5 of Decay

Energy of RadiationIn Mev

Assignment

SbM3 n, ~ ) (th

IT 7
0.012

Sbw3 (th n, y )

WI

B60.4 d

P-

0.202, 0.36, 0.608,

O.~lJ 0.930, . 0.632, 0.967, 1.70, o.3oo, 0.175, 0.377, 0.637 1.591, 0.645, 1.05, 2.09,

0.745 1.658 0.713, 1.33, 2.3 0.612 0.214 0.463 1.37,

SbM3 1~

(th n, 7) (fastn, ~ )

0.603, 0.722, 1.45,

2*O y

BY

0.u25, 0.113, 0.320, 0.595,

0.444, 0.205, 0.427,

(nJf) (pilen,

.+24

7P) ?

d 9.4d SnU5

III. TABLE OF ANTIMONYISOIUPR3 cent d

Type Isotope ~ Half-Ldfe P7 of Ikcay

Energy of Radiationin Mev T

0.65 o.h.2, 0.% 0.417, 0.685, 0.90

Assignment U (n,f) T# (fastn,p)

P7

U (n,f) *1X3 U (%-W u (n,f) u (E6-Mevd,f) P 9.3h Te1n a p 105 Te~~ (787) (*) , (~70-Mev ~fl,n) ? d,f)

1.10, 1.35 137 1.11, 1.50 0.60, 0.248, o.3io 0.463, 0.772

P7

2,9 0.32, 0.75

U (n,f) Telx (njp) ~e130 (%kkvd,u) U (n, f) 0.75, 0.90 ? Telx ~e~o (n, p) (28_M~ d ~) ?

lg+$

s-b i--

9.9 h

P7

1.0

0.32,-0.4,

III. TABLE OF ANTMONY ISOTOPES- cent d

180tope &#9

Half-Life
4.6 h

of Jkcay

I
1.~ I
0.165,

Energy of kdlati~n in Mev

Assignment Ii (nJf)

(~)

others
0.534, 0.7WJ

0.308,

P6F !cel= (76f) ~3X WW (24$)

33 m

13-

U (n, f) @30 (~ p)

7.1 m -1

U (nJf) ~lw (n )

23,1 m

B-

IJ(n, f) 1 P 25mmW p 1.2d Tl@ (851) (15*)

Sb132

2.1 m

P.1

U (nJf) P7 8h %132

4.1 m

U (n)f) P5Pfi p @@33 133 (94) (8$)

III. TABIE OF ANIR40NY SOTOPES- centd I

180tope

Half-Llf e

Type Of Decay

Energy of Radlatlonin Mev

Assignment

Mass and haM- lif assignmentsare uncertain. See NationalResearch CouncilNuclear Data Sheets e %-1%-1 NRC 5&8-11 for discu6Bionof as6ignment8.

Sourcesof data used, this compilationand to be referredto for additionalinformationwe as in follows : 1. Nuclearlkta Sheets,NationalAcademy of Scienc= - NationalReswch 2101 Const itut ion Avenue, Washington25, D.C. D., Hollander,J. M., Seaborg,G. T., Rev. Mod. Pbysics~ 2. Strominger,
3. suvau, w. H., T!riklneer lwt of Nuclides (1958 and r@lsions), @t. C

Council,

585 (1958). of ~c~ents,

U. S. Gkrnment

Printing Office,Wasklngton25, D.C.

Iv. IV-1 . OIZDATION mm

GENEFML CHEMISTRY OF ANITMONY

Other than the metal, the ccmmon oxidation statea of antimony me

-3 In 9bH3, +3 in Sb203, ui +5 in sb205. Cldnm made for the exiBtence

Of ~205

and the stabilityof 13b20b indicate a +4 crystal~ne 8tate

also. Iatimer2 summsr izes the oxidation-reduction potentials of the couplee aa: 0.51 % Sb -o..212
~+ -o.6a sb@4 0.40 25

(Acid)

-0.581
(1.34) sb~ Sb 0.66 ~2(0.40) ~9b06-4

(Baae)

Reduction to the metal is easily performed with Pb, Sn, Bi, Cu, Cd, Fe, Zn, S.ndl.fg. .mme cases where the metals evolve hydrogen from In and dilute aci~psz%ial reduc+ion to SbH3 may occur3. K,Jelbert P8ppas4 used chromous ion for reduction in a radiochemicalprocedure (see Antimony fiocedure No. ~ Section VIII). Robinson and Milton5 separated

antimony from irradiatedEnC$ by depositing it as the metal on copper from an acid halide solutionwithout the use of external current. Under the best conditions a yield of 71$ 18 reported. In the an.alybical aboratory,antimony la coxsonly found as the +3 l or +5 salt. Metalllc anthony is easily oxidized to Sb(III) and to as high as +5 by BN03~ C122 Bra h(VI), Mn(~), and other strong oxidants,

depending on the amount of reagent aud temperature. Iodine oxidizes E% to Sb(III) and in alkaHne solution Sb(V) mRy form. Antlnumlc compounds are reduced to the +3 state by SnC> tion from As) and NaM#02. IV-2 EIIMINTALANIIMORY ACCOrding to Sidgwick , there are four aolld forms of antimony 1 metal. IV-2.1 YellowAuthnony. This form is tramsp=ent and soluble in carbon (distinc-

disulfide. It is evidently covalent end correspondsto white phosphorous ad yelhw arsenic. The action of omen on stibine at low temperaIs

IV-2.2 Black @ttiny.

tures or the rapid coo~ng of antimonyvapor gives this form. W

formed from the yellow species and is more chemicallyactive than the ordinary form.
iv-2.3

MetalMc Ordln or q

Anttiony. This form is truly metaldlc,

melting at 630c. IV-2.4 E@osive

and boiling at 1325C.

Anttiny.

The electrolysisof antbony trichloride,

tribromlde,or triiodide with high current density produces this form. On heating to ZQOC. of scratching,it changes explosivelyto the ordinary form. IV-3 OXIDES OF ANITMONY !Cbree oxides of the element exist, Sb203, Hb@4, ad Hb@5. The

trioxide along with some tetroxide is formed when the metal. burned in is EeatSng the trioxide in air to 300-400C.forms the tetroxide; BllJ7. however, at higher tempmatures (i.e. gOOC.) it decomposesback to the I trioxide. The trioxide is ezaphoteric,t M.molves in concentratedacids and basic salts are crystallizedfrom solution. The basic antimonyl (&IO+) salts are hydrolyzed in hot water. The trioxide also dissolves in alkedles forming salts of anttionousacid such as NaSb02-3H#3. The tetrotide is acidic in character dissolvingonly in basic solutions. The pentavalent state of antimony may be prepared by the action of HN03 on the trioxide. The oxide and correspondingacid, H9b(OH)6, me only IV-4. slightly soluble in water but readily soluble in alkali. HYDRIDE OF ANTIMONY om.% one hydride, ~E3, iS ~. It is easily prep=ed by

cathodic reduction or by reduction of antimony compounds in acid solutionby strong metal r~uctents. The generationof stibine as a

mesms of separatingantimony from fission product solutions is presented in Sections V-3 and VIII, Procedures ~ and 4.

10

IV-~. SOLUBLE CCMRIUNM The soluble compounds of =timony 22,23) 24 me given in Table 1. TABLE 1. . salts
sbBr3

SOI.UKLE -OIW

sAI.rs
ml.

Solubiuty in g/loo
SQu!2Q -

Other S. HC1, EHr, CS2, 3 . acet. S. al., HC1, tart. a., CS2

d.

d.

sbc13

601.6

sbc15 SbF3 SbF5 SbI 3 &H3 Na3sbs49H@ K3SbS45H.# Li3sbs4. lo~o (m)3sbs44H@ (SbO)KC4@06;@@ sb(c.#D@@3 sb2(C4H406) 36H@
IV.6.

a. 384.7 s d. .20cm3

d. 563.630

S. HC1, tart. a. NH 3 s. KF S. HI, HC1, D, al., CS2, acct. 1500 cm3 al. 25ca CIU3cs 2 S. NaOH S. KOH S. ale. i.

d. 4 Cms

27.130 75.13 50.130 54.530 5.39 m s.

57.1~ 79.P

35.71~

s. gly i. eth.

rNsoixlBLE Cmfmxmos Of the many Insoluble salts of antimony several have been used

for gratietric determinationsand to establlsh procedures.

IV-6.1

yields

in rtiiochemlcal

IQdroly SIS Prcducts. Except for the fluoride and some organic citrates), aU the salts of +3 Sb are

co&ounda (e.g. tartrates ad

hydrolyzed,wblchis often overlookedby the analyst. The chloride hydrolyzesto Insolublewhite oxychloride,the compositionbeing dependent upon the emokt of water. The precipitate is soluble in IJ

solutionsof tsrtaric acid, strong HC1, or excess alkali halide due to complex formation. washing the precipitatewith water slowly convertB it to the oxide. With SbC15, the basic salt is thought to be SbOC13,

but the formula has been questioned. IV.6.2 Oxides. The Wti bhydroxides aud carbonatesprecipitatewhite,

sb203 from acid 6olutionsof anttinous salts. The precipitate

is soluble in hot solutionsof excess alkti but insoluble in NH40H. If an alkallne solution of Sb(III) is carefuJJyneutrtized with acid (not HF, citric or tartaric) the oxide is precipitatedand at once dissolved by further addition of the acid. Freshly precipitatedSh203 is soluble is oxalic acid but a precipitate soon forms unlesB excess alkali 3. The oxide or oxalate is present to form the soluble double oxalate hydrated oxides are precipitatedfrom Bolutions of fixed antimonites or anthnonatesupon neutralizationtith HlV03 other ~neral =ids bqt or the freehly formed precipitatewill readily dissolve in exceBs acid. A pavimetric procedure of weighing the tetroxide resulting from ignition 26 of the sulfide is discussed by FMllebrand and LundelJ . Iv-6.3 SuMldes. Hydrogen sulfide precipitatesthe orange-red stiide,

Sb2S3, from dilute acidic solutionsof Sb(III). In neutral solutions (t@r@te present), precipltationis incomplete. No precipitateforms
The

in ftied alkali solutions. water; Insoluble In (~)2C03

stiide iB slowly decomposedby boillng

(distinctionfrom As); S1OWIY soluble in

boillng solutionsof ftied alkaM carbonates;soluble in cold concentrated and hot 1:1 HC1 (distinctionfrom As). The orange antimonic swide, Sb#5, is precipitatedtier s~,COnditiOILS.This suHide

has the same solubllitlesaa the trit3UJfide except that it is soluble in NH40H3. All salts of antimony when boiled with Na#@3 as the sulfide. Iv-6.4 Complex SuJfide. A 6olution of ethylenediamineand chromous chloride yields the complex CrNH2(CH2)@H@S4 which ,~s been used for precipitate,

the micrugravimetricdeterminationof anthon@.

IJ?

IV-6. 5

Silver

Antimonate. Antimonatesprecipitatewith AgN03 to give

white AgSbo3 which is soluble In NH40H. A silver salt alao fO~S tien SbH3 is bubbled through a silver nitrate solution. The silver reduces and the anttiony coverts to the oxide (or acid) which is only sllghtly soluble in H20 (distinctionfrom AS)3. IV-6.6 Tbioaal.ide. Anttiny(III) can be separatedby precipitating Sb(C@1@Ns)3 fi~ either acidic or basic solutions. Chloride and
hsic

sulPate interfereby causing the formation of

salts. Arsenic, Bi,

Z?3 Cd, Au, Pb, Hg, Th, Sn, and the alkaline earths also precipitate . IV-6.7 8-Hydroxyquinollne. The yellow complex Sb(C#T@N)3 quantitati?rely precipitatesfram acidic solution as the pH Is increasedtoward 6. This complex is stable at 105-1100C.and maybe used for the gravi-

28 metric determinationof antimony . Since many .otherions a-o react with this reagent, a preseparationis required. IV-6.8 TrIphenylmethylarsonium Chloride. -S , mdFiggis3

recwnmend axsonlum halides, especiallytriphenylmethylsxsonlum chloride and icillde, for the determinationof Sb as well as for Bi and Cd. A simple ion associationcompmnid triphenylmethylarsotium etrachlorot antimonate(~l) is formed. As little as 10 pg csn be determinedby nephelometryand larger amounts gravtietrlcally. Iv-6.9 w% allol. Feige131 discusseg the precipitationof antimony excess of pyrogalJol in air-free water is

with pyrogald.ol.A @ge

added to a dilute acldlc solution for analyais. Welcher33 ~sts 1.8 other elements which cam be determinedby tbls reagent. IV-6.1O 9-Methyl-2.?,7-Trihydroxy -6-F1uorone. Feige132 discussesbriefly the work of Wenger33 who recommends 9-methyl-2,3,7-trihydroxyl-6-fhxone as a specificreagent for amtimony. The compound is soluble in alcohol. A red coripound with antimony salts forms In strongly acid solutions. It Is probable that the complex can be extracted.
IV-6.11

~ferron.

Several elements are precipitatedwith cupferron

from strongly acid soltiions32. The only antimony oxidation state that

completelyprecipitatesis +3.

The pentavalent state does not precipi-

tate. For speclficlty,a presepexdion is required. IV-6.K2 a-hli~p~ idine, An orsmge-~llow precipitateof antimony is

formed with a-aminopyridine33. As little as 0.12 ug. is detected. Bismuth, Co, Cu, Au, and Zn interfere. Iv-6.I_3 Fhenyl&lohydan oic Acid. Several metals, IncludingPb, Ag, t Cd, Cu, Co, and Sb exe quantitativelyprecipitatedwith thin reagent. The precipitate forma in dilute acetic acid after boiling for about 5 minutes. Welcher33 gives a detailed procedure for the determination of antimony but tt appeers to offer little advantageover other methods. IV-6.14 Methyl Violet. Antimony(V)is precipl.tatedithmethyltioletU. t 46 Poper45 reports similar findings. Goto and Kakita have extracted the precipitatedcomplex into emyl acetate. Several other organic reagents have been proposed for the detection of antimony. me 44 reader ia referred to Welcher33 and Feigel for more

conrplete listings. O IV-7. VOL4!lIUE CCMPOUNDS AND DIS!ITILATTONF ANTIMONY The volatilizationof elements as bromides and chlorideshas been extensivelystudied by~f~ ~ndeU81 . Both Sb(III) and

Sb(V) are quantitativelydistilled as the bromide from HC104 or H#04. Antimony does not significantlydistill as the chloride from HC104, differentiatingit from Sn(II) and Sn(IV)81. Arsenic(III)and Aa(V), Re, and Ru also distill from an H6r-H@04 solution. The volatile hydride, SbH3 is discussed in Section ~-4. Use of

the volatile halides and stibine in analytical separationsis discussed In Section V-3. IV-8. C~IEX
~t~odIII)
or

IONS AND CHEMD?S

hti.e

comphexes~~-

and[sb~= tith x

. .~

F-, have been reported. Hexahalo complexes,correspondingto

bF6 [1 ere also known35. The bromide complex differs

Pd E%lfrom the chloride and fluoride by being highly colored and easily

14

hydrolyzed. A heptafluoroant~ny ion of unknown structure is reportedl

for the salt K@F7.H@

lbth Sb(DI ) and Sb(IV) form chelates with catechol. Undoubt ably many of the organo compounds described in Section IV-6 are also chelates. Mttle use has been made of complex lone and chelatea In radiochemical procedures for antimony. Ibth shople ion-associationcompomds and chelates are
e-i~

extracted in organic solvents and can form the

basis for selective sepexations. IV-9. ISOTUPIC EXCHANGE . REACTION SANDHOT-ATKM CHEMISTRY Berker and Kabngg studied the rate of exchange of Sb between SbC13 & 9bC15 in CC14. The rate of exchange la both time and Ilght of the reaction was 235 of Sb(III) and

dependent. At 50C. and 81C. the half the

hours and 19.5 hours respectively. The rate of exc~e

Sb(IV) in HCl solutions accordingto Bonnerloo Is a function of HC1 concentration. The = ttie of the Peaction is lh hours in ~HCl,

60 hours in f&HCl, and 36 minutes in l~HC1. 101 studied the Szil.scrd-Chalmers reaction with both Melander phenylstibinlcacid and triphenylstiblne. No concentrationof Sb activity was obtained from the irradiatedphenylstibinicacid. A concentrationfactor of 100 IS obtdnable by irradiating (C6H5)3Sb in benzene and extractingwith aqueous 2$ textaxic acid, 0.05$ KSbO taxtrate. Concentrationfactors up to 6000 axe reported102for the slow neutron irradiationof (C6~)3 Sb in benzene followed by tiraction with 2.% Hcl. Large concentrationfactors have alm been obtained by irradiating solid triphenyl antimony compounds,dissolvingthe target in chloroform and extractingwith au aqueous KHa tartrate solution103. The reaiL=r is 103 for a nmre detailed diacuBaion of hotrefemed to Wehl and Bonner atom chemistry.

15

v.

JmAmmXL m

cmmsI!RY OF ANmMoNY APHZCABIE YIELD DErEmmAmm

sEPARA!lzomm

v-1.

SOLWENl! EXTRAC!KCON Solvent extractionprmldes rediochemistswith a rapid and almple

technique for the selective Beparetionof an element from complex mdxtures. Through the judicioususe of various scrubbingagents and str~ppants,igh de~ees of separationare attainable. The simplicity h , of the operationrenders tbls technique easily adaptableto remote operation. In many instance~the entire sepexationmay be performedcm a cexrier free basis thereby eliminatingthe Itierent errors, such as coprecipitationand non-stoichiometric relationdlps, associatedwith ~atietric yield determinations. Because many extractablecomplexes

are colored, the @eId, if required, can in many cases be determinedby a simple apectrophotometric measurement. The use of deep well crystals and gamma spectrometrycombined with solvent extractionseparationsemd spectrophotametric yields is gaining popularity in radiochemistry. V-1.l Ion-AssociationSystems V-1.l.l Fluoride System. Extraction studies of fluoride ~yatems are 36 studied the extractionof several elements relatively few. Kitahara fram EF solutionsinto ethyl ether. The extractionof Sb(III) from 3.~HF is reported % 37 to be less than l? as is the extraction of Sb(V)

from m_HF

. Iarge quantitiesof 9b(V) can be extractedwith diethyl in KF with the extracted

ether from an aqueous phase 6M in HC1 and O.&

species probably being the chloride ratlkr thau the fluoride complex. V-1.1.2 Chloride System. Factensive reviews of the extractionof the ch~ide
38,39,40. complexesof 6baxe available ~wds

@voigt41

have shown that the extractionof anthony Into isopropyl ether IS superior to that of diethyl ether. The distributioncoefficient iB greater than ZQO for Sb(V) from 6.5 to 8.% HC1. Excellent separation

16

of Sb(V) from Sb(III) is achieved. Schweitzer and Storms

43

confti these

findings Complete extractionof Sb(V) and 681 extractionof Sb(III) . 42 from HCl ~olut ions with methyllsobut l ketone has been reported . The y extraction,and sepexatlonof Sb(V) from sev=al elements, from 1 to ~ into ethyl acetate has been HC1 containingoxalate and tiltrate

reported by White and Rose47. Iron, Sh, Cu, Cd, Pb, Ge, and Te are not extracted;As, Bi, and MO extract in trace amounts; Ag and Hg partially e.xtract~ and Au completely extracts. The separationof Sb from S% oftentimesdesired in radlochemlcal separations,can be attainedby extractionof Sb(V) into ethyl acetate from @ HC149. Tin(IV) remains in the aqueous phase. The separation,

by extractionInto isopropyl ether, is reported by Coombem. The 47 procedure of White and Rose mentioned above is SMO app~cable. TrI-n-octylphosphine oxide in cyclohexaneextracts antimony(III)
from @

48 HC1 with reasonable separationfrom several other elements.

The extractionof Sb in chloride systems, though shnple, is a poor system because a Wge number ofchloride complexes of other
sequestering

elements also extract. The use of

agents, both In the

original aqueous phase and subsequentscrubs, contributesto a cleaner separation. Passas

64

developed a rapid (~5-min. procedure for the )

sepsxatlonof short Uved antimony isotopeg from f!reshly irradiated

uranium by extraction
of the chloro complex into isopropyl

ether.

Molybdenum which 4s0

extracts is retained in the organic phase by

format ion of the blghly soluble tbiocyanat complex. e V-1.1.3 Brcmlde Systems. ??ock, Kukche, and Bock51 extensively

stdied the extractionof various elements from HSr. Ninty-fIve per cent extractionof Sb(V) from ~ HSr into ethyl ether is reported,

the extractionof Sb(III) Is considerablyless. Gold, Ga, In, As(III), Tl, Sn(lI and IV), Mo(VI), and Fe (III) extract to @eater them 50~ frcm4toq BEm. The same general comments given for the chlorlde

system regarding epecif icit apply to the brcmide ,sstem. y y

17

V-1.1.4 Iodide System. Iodide extractionsystems have been more ) extensivelyatudled them brcmdde. Antimony(III quantitatively extracts frcm 6.~ HI into ethyl ether as do As(111), Cd(II), Au(III), in 0.7%

In(III), Hg(II), Tl(I), T!L(III), and Sn(II). With l.%~

52 H404, less than 50$ of the antlm.ony extracts into ethyl ether . West53 states that small amounts of the tetralcdoantimonate (III) ion extract
into

benzene frcpra H2S04-KI aqueous phase.

V-1.1.5 TblOc ymate System. Slight or no extractionof Sb(III) into ) 54 ethyl ether from O.% HC1 contacting UP to ~ ~4~S has been observed . a Tin(IV) quantitativelyextracts Ilrom similar media suggestinga possible separation.
v-1.1.6

mlphosph

oric Acids. Less then 5? extraction of Sb(III) &

Sb(V) with O.% dibutylphosphoricacid with greater than 95$ extraction 39 of Sn(IV)J W, Nb, Y, and In is reported .
V-1.1.7

oxide, llrialky lphosphineOxides. With tri-n-octylphosphine 48 HC1 . Complete extractionof

Sb(III) partially extracts from ~

Sb(III) is reallzed by increasingthe HC1 concentrationto ~. v-1.1.8 Methyldioctyhnine. Extractionof antimony from greater than @ HC1 is quantitativewith 2 to 3 volume percent solutionsof

50 methyldioctylaminein xylene . The extractiondecreases with lower HC1 concentrations. V-1.1.9 Quarternarymimes. Work in progress In the adhors laboraA tory pertaining to the quat ernsxy amine extractionof the elements shows that both Sb(III) and Sb(V) are completelyextracted flmu,~ HC1 as the tetrabutylenmoniumchloro entlmony complex into hexone. Little or no extractionwas observed in BN03, H#04, V-1.1.1O Rhodamlne B.
~, or NaoH s~t~.

The chloro complex of S%(V) forms an ion-

associationcomplex with rhodemine B readily extractableinto benzene or ethyl acetate fram 3 to ~ HC1
39

. Severti investigators55~ 56>57

describe modified determinationsof antimony. Recently Vanhnan et. al.66 described a colortietrlcrhodemine B procedure which eUminates hydrolysis
la

problems encounteredIn other methods. A relative stud 1.Z$ Is reported for the range of 2-XI ug of Sb. V-1.l.ld Methyl Violet. AntWny(V)

deviation of

forma a precipitatewith methyl

46 violet inEC1 which is soluble emyl acetate . The sensitivityof in

this system is 0.1 ug./ml. Jean @

describes the etiractionof the

violet blue complex i%cm @ V-1.1.12 llzo~.

HC1 into benzene.

Morrison and l?ceiser39 Ilst several azo dyes which .

form ion-associationcamplexeswith ~(V) in strong HCl - saturatd ethanol media extractableinto benzene. Generally the reactions exe quite sensitive (1-8 ug./ti. of %). V-1.2 Chelate Systems V-1.2.1 Cupferron. Cupferronhas been used for the separationand determinationof,several elements. The insolubleprecipitatesformed with cupferron pre soluble in organic reagents such as etherand chlorofomn. Ant~ny(III) is quantitativelyextractedtid chloroform

39 frcm 10$ H2S0462. Several other elements also extract ,. V-1.2.2 Sodium Diethyldithiocexbemate.A ~ aqueous solution of this 9.5, ~(111)

39. BetweenPE4to res8ent till extract abut ZU elements

extracts into carbon tetracbloride. CiFradiochemicalinterest,As(III) and Sn(IV) also .artract.Use of masking agents such as EDTA and cyanide have greatly increasedthe selectivityof this reagent. v-1.2.3 Morin. Anthony(III), in addition to Al, %, Ce(III), Ga, In,

Sc, Sn, T!h,Ti, and !Zk, form complexeswith morin, extractableinto butyl, .sm@, and cyclohexyldCOhOl frcm ECidiC media39. v-1.2.4 8-w nolinol. The precipitationof entimony with 8-quinolinol has been discussed in ~ction IV-6.7. It seems reasonable to aasume

that the compl~ is orgemic soluble and extractable. The re~ent also reacts with about hO other metals39 . 65 V-1.2.5 Potassium Xanthate. Islein and Vorbes report the extraction of Sb from acidic solutionsinto carbon tetracbloridewith potassium 39 xanthate. Less metals are reported to react with tbls compound

19

compwed to the o#her chelates. Further investigationof this system appears warranted as an extractionprocedure for the separationof Sb in fimion product mixtures. v-1.2.6 htip~ Ine. The separationof Sb frcnn Bi, Big,Sn(IV), As(III), 65 Zn, Co, Ni, and & has been reported for a chloroformsystem . V-2 CHSOMATCGRWEY . AIW?IMONY OF

V-2.1 Ion-Exchange V-2.1.1 Cation-Exchange. According to Lure and FYlippora , entimony .1sseparablefrom =senic and tin bypasmge of a dilute HC1 solution
6a

through the sulfoDIc acid cation exchangerWofatit-P In the hydrogen form. Arsenic passes through with Sb and Snremalnlng tight~bound. Bismuth 18 reparableflrom as the thiocymate 6a3 the aepuation being Sb made with a 6$ solution of NH4CRB O.% in H2SOL. Autimony(III)CaU be

separatedfrom Sn(II) on AmberEte IR-12Cl elution with O.% HCl by 69 contelnlng @ tartaric acid . Autimony(III)elutes, end Sn(II) rmalns on the column. Antimony(III)and Sb(V) c=be separatd by

70 elutlng Sb(III) with dilute oxsJlc acid . The unexpectedadsorption of negatively ch=ged chloride complexes,IncludingSb(V), on a cation exchanger has been reported . V-2.1.2 #mlon Exchange 71 V-2.1.2.1 Chloride System. fiaus and Ifelson extensivelystudied the anion exchange propei%ies of the elements in HCl with Ibyex-1. The distribution coefficientof Sb(III) is greater than 103 in ~ HC1 while
67

that of Sb(V) is less than 10. Separationof Sb(III) and Sb(V) IS difficult due to the slow rate of desorptlonof Sb(V) with dilute HC1 elutrient and the hydrolyticproperties, Sb(III) in dilute HC1. of Trace amounts (Sb124)indicate that Sb(V) Is not adsorbed on Dowex-1 in dilute HCl whereas Sb(III), formed by reduction of Sb(V) with H SO 2 3 7 is strongly adsorbed . me seperationof Sb(V), Ta(IV), and Sn(IV) 72 using a Dowex-1-X4 column has been reported . For other possible sepsxationathe reader Is referred to the summary paper of fiaus and 20

,,
~e180n71

for a table of the di8trlbutioncoefficientof the elementB.

V-2.1.2.2 Fluoride System. FwiS73 has studied the fluoride-anion exchangepropertied of the element8 Eimilex to that described above for chloride. Antimony(III)1s strongly edsorbed in dilute I-E?; Sb(V) appe=a strongly edsorked at all concentration. Arsenic(V) as well as Sn(~) exe also stronglyheld. Arsenlc(III)IS not adsorbed offering same possibilityfbr the separationof As and Sb. V-2.l.2.3 Nitrate System. l?eris
80 has alJ3o studied the anion exc~e

properties of the elements in nitric acid on IkIwex 1. bthnony(V) and As(V) are not adsorbed w Sn(IV) Is slightly adsorbed. This syB~em

aple=s to offer uttle advantege for the separationof Sb from other elements. V-2.1.2.4 Oxalate System. Mixbres of &(IV), Sb(V), end Te(IV) are 74 separableon a Dowex 1 column . The sample in ~ acid is placed on the column. Telluriu@V) O.~oxallc HC1 - O,~oxalic

is eluted ftist with 4.8 sodium

acid, then antimony is separatedwith O.~pH H#304.

oxalate, finally tin is removed with ~

V-2,1.2.5 Malonate Sywtem. The separatimof

tracer Sb(V) and Sn(IV)

using emmmium malonate as the elutriant on an Amber~te IRA-400 column @s been described 75. The Sn(IV) malonate is retsined on the

column while the anttiony iB eluted with a 3$ malonat ~olution at a e pH of 4.8. V-2.1.2.6 Tin is removed with 4.% H&04. S~ide. The separationof Sn, As, and Sb as sulfide com2 columns has been studied. A 3$

plexes in basic solution on kwex sodi~ polys~ide

solution is placed on a.Dowex 2 column in the is removed with O.~ KOH. KDH, arsenic with l.~ KOH,

hydroxide form. Hn and antimony with 3.% V-2.2

ic Inorgan Alumina Exchagem Numerous procedureshave been developed for the =Peration of

elements with an alumina column. Generally,washi~ with selected solvents separatesthe elements into bands which are identifiedby

w
color lou&

reewnta form to colored

frdn H# Sb(III) saturatul vith water.

Cqlexel%
with dilute

*S-C ~

(III)

C=

.be
the endthe

separated

by waehins

ahd develpplng Is yellow

The ~ea 77

(AE). =

Sb(IZI) baM

is mange-red. .

Antimmy cti bermu+edfrcmt he

elcmenta of the tin ~oup by addition ae a ~a$ solution ti waehing

with dilute HC1??. Arsenic is

eltiai Mth

a H@

Baturtitd eolutiun

-mvesdown

thecolumnaeq

Mamn yellow band. Fallmdng the 19 r&mved with.co~entrated:MHl@H. &, eluted. SeleOilumJ. Te, and MO are

deaorption of srsmlc, antTin, Tej and MO are ~ttally

completelyrewved by waeldng tith a solution of 8tJare aepmated; & and Sb wp=ation ie @or.

(qj2s.

Arsenic d

W reader 19 referred

to Lederer end.kderer79 for a nmre ccmplete discuaaionof inorgahlc ~a.

V-2.3 .RzPer Chromatogm@JY thie tecbnlque ccmimta of dipping the end of a filter

:.

GeneralQ

pwer

strip intu the ample solution. The fona migrate qp the paper
ae the eolvent

variablea vith clumacteritiicratea dependeqt on EIuch

media, pH, &Ltype of paper. In many caeee,

AI.(OH)3 a an ion~ The pap= hewebaan may be 8p3yed

papera

@.P%Pe .tad Uith thG. de~ee of

imdtoincreaaa ulth CO*

separation.

fozmihg reagent8 or

aectionecut out fbr.aubaequentquantitative-la. Many ueeful aeparationeof Ae(III) d

contracted

Sb(III) have been reported

to fev for 8b and Sn79. In a butauol-HClm@ia~. Ae la Sn. The separation

the lower of Aa(III) end Sb(III) of haa

aeperatedfran Sb ad
been 8b(III), .sccaqUehed ti(~) with

eJcohole79.

Separation

Aa (III),

has bB-.

ObtdJled

with COIJldime. aaturated . wI*

o.&J Elm .
v-3 3 mILKlzmw me vOktile m antvOLmIIzzA!IT@!J c~unde have ken ,.

demribed .in6ectimn IV-T.

deecri-a schemer -13enic, ent~, d

a-dlatiUation poceduru far the separationof tin. !llhe aauple is ,placedin the titillation 22

flask end made @in at lJ1-lJ2C. me

EUl and 0.5 to ~

in H#04.

Arsenic is distilled

receiver iB removed, phosphoric acid 18 kdded the to

dlstilJlng flask, and antinxmy 18 distilled at 155-165C. After cooking; the receiver Is changed and the distillationis continued
at 140C.

with a 3 to 1 mixture of concentratedHC1 and concentrated

H&

dropping into the distllJlng flask. MolyMenum, Re, Se, Te, and

Hg pertialJy dllstill. Radloanthony is mphrated by distitition inProcedure~ de-

scribed in detail in Section VIIC. Heti.83 describes a &upMfied distillationprocedure for Sb, As, and ~and Maxwell et. al.84

describe the distillation of Sb from HCIOk-lIEr.The easily &ccomplished electro~ic formation of stibine, SbH3, has been used as thebasis Cook13 separates anttiny from

for the separationof radioantimo~.

fission prcduct mixtures by generating stibine at a lead cathcde in an atnmsphereof hydrogen. The stibine, swept out of the cell %y the -Wen stre~, Passes thro@ a sl%htu acid silver nitrate solution, anthiotide.

forming a mirror when heated or remaining As ihsoluble sll~

The latter technique is more convenient. Inve93, using this techmlque, recently described a 10-secondprocedure (SectionVIII, Rrocedure 4) for aeperatlng short-~ved antlmohy from fission product mixtureB with Other methods base&on gerieration greater than 107 decontaminatlori. of stlbine have been reportedm#15~~/17~~. V-4 =ECI!ROC=SIRY OF . ~

V-4.1 Electrodepasition One hportent advantage of electrodeposition compared to precipitationiB that extraneousIons are not added which can interfere in subsequ~ntanalytical. steps. Controlledpotential techniquesprotide specificity,with completenessmd apeed of separationprimarily

dependent upon the differences in the reduction@tentials of the lonmetal reactionB. The techmique Is particulerJyadvantGgeoue for radlochemicalapplicationbeca&e thin @l evenly deposited films on

23

cells, and counting plates axe obtainable. Details of instrumentation, 8 general. methodology -e fuJJ.y demrlbed by Idngane . Reynolda6 extensivelystudied the controlledcathdde potential itatlve recovery was separationof antimony,tin, and bismuth. Quark obtained from a sulfuric acid - hydrazine stiate solution at -0.3 V. Jovanoticg studied the cathcdic depositrlon bismuth and emtlmony from of H#O~ media and give, procedure. for their sepsxationfrortln. 25 Nornitz also,diacuesesthe electrolyticdeterminationof antimony. Several comprehensivestudies of controlled- potential electrodeposition have been reportei recently. Tankam describes the electrdeposition behatior of antimony in HC1, H#04, HN03, MH40H, and cyanide media. The controlledpotential separationand determinationof antdmony, copper, led, and tin in nonferrous alloys is dlscuasedby U Hayakawa . Electrodeposition has been used in several radiochemicalseparations. A methcd for the sepsxatlon@ mounting of antimony as well as

several other elements is described by Lee and Cook7. Excellentbeta coumting plates, mitable for decay scheme studies,were obtained. Her# isolated the separatedantimony Rrom a Szilard-Chalmers

reaction by electradepoaition a platlnus electrode. on Hydrogen canbe likerated In snelectrcdeposition technique aud cme must be taken to prevent the 10BB of entimcmy as 9bR . 3 v-4.2 Polar~aphy Polarcgraphyhas not been used for the radiochemicaldeterndnation of antinmny. lblthoff and Idngane discuss several polsxographic 19 methcds for the determinationof antjmmy in complex mitiures. Excellent waves are obtained in ~ a half wve HN03 with gektin as a maximum suppressorwith

potential of -0.3 V. vs. S.C.E.

Love= has been pioneering the applicationsof polarographyto radiochemist~. Antimony has not been Investigated;however, tihe

technique may be app~cable to the separationof antimony from fission prcduct mlxturea. 24

v-4.3

Jllmlgams

Isotopic excbmge with mercury amalgams has been proposed by 21 Meinke as a technique i%r the separationof radloelments from complex mixtures. Attempts to prepare an anttiny-amalgsm were unsuccessful. V-5 GRAVIMIIFRY Volumetricmethckls for the msn-radiochemical determinationof antinmny axe accurate aud rapid, hence the more tedloua gravtietric methods are seldam used. Precipitationas.the .s~ide has been used almost to the exclusion of other methods. (&e Wction IV-6 for a compiktion ofprecipitants). However, disagreementexists concerningits use. Hillebrand and 26 LWndel.1 state that weighing of the trlsulfide is satisfactoryif it 25 Is drfed and heated In an atmosphereof C02 at 280-3C0C. Narwltz cl.aha that errors inherent in depositingthe sulfide frcm acidic solution include adhering deposits and inmmplete precipitation. Results can be 1 to 1.5% high due to occlusion of oxygen and .miUur compounds . Although sfiide precipitationas a means of determing antimony requires precise conditions for accuratemacro analysis,the errors

involved do not appear to be of such consequenceto seriouslyaffect yield determinationsin routine radlochemicalanalyses. Yield determinationsfor many elements are sub~ect to shilar conditions of occlusion and non-stoichiametric precipitation. fie author believes that other more precise analyticaltechniques, such as titrimetryor spectrophotometry, are better suited for @Xld determinations. The increasinguse of gannna spectrometryaud especiallydeep well counting encomages investigationalong these lines. v-6 SPEC?lZROPHOT@lETRY This proven technique can substitutefor gravtietricfield determinationin many radiochemicalmethods and cticumvert such errors as coprecipitation, occlusion, and questionableformula of Ignited

25

product s. It iB a simple matter ta develop the color by addition of u chromogenicagent, make to volume, remve an aliquot for the absorbance measurement,and count the remainder. An example of this, uelng rhcdemlne B as the chrcmqenic egent, is given in Section VIII, Rtocedure 4.
Rhcdamlne

B is the most widely used re~nt

for Sb. Sandeli85

discusses the merits and shortcomingsof the method. For qtititative recovery, the crucial step in the rhodemine B meth~ is conversionof Sb(I~) to SbC16-. The HC1 concentrate must be greater than ~ ion and

Ce(IV) appears to be one of the few suitable. oxidizing agents. Because SbC16- slowly hydrolyzes,the rhodemlne B is added i&n&liately~er oxldat ion.
The

precipitate (bright red) 16 easily extracted into and

m organic solvents,providing addit ional decent eminat io,n. Luke 66 Vadmlan report a@ht modificationsin the procedure.

In acid solution, strongly,yellow colored Iodoantbonlte is 86 formed by addition of excess Iodide to either Bb(III) or (V) . BeerIs law is followed for the range of 5 to 50 ppn of enthmmy. Nitrite, hypochlorite,end suEite interfere end close control of iodide end acidity must be mainteined. A pyridineantimony has been described by Clarke87. In this icdide pr@edure, methcd for

pyridine

forms a sll@ly

soluble, colored todoantimonitecomplex, which is kept mid concentrationfor -m

in suspension.bygum arabic. S~iC

color intensity is 3 to 4M and iodide and pyridine concentrate ions must be closely controlled. Methyl violet, bril.llant green, and enthraquinone--azo1 ddmethyl auillne react with emttiny(V) in a ~er r~ne v-7 m~Y Titrimetricmethods also offer conveniencefor detemning the ~85 . similar to

yield in a rtiiochemicalmethod. The entire separated sample can be titrated, then counted in a well tryst al. Usuallyantimony is determined by oxidimetrictitration of Sb(III)with p&manganete, iodine, or br~te.

26

Cerium(IV)

and di.chromate

can also

be used.

!lltrat tith bromine iB usually c-led ion

out at an elevated

temperaturewith methyl orange or indigo sulfonic acid ag the indicator. Antinmny(III)can be titrated with icdine in concentrated bicdxmate solution. Tartrate add~ to hold the anthnony in is

solution. The reaction la slow nem the eq~valence point and offers 89. In the presence of HCIJ no advantagesover the brcnnate titration Eh(ITI) IS oxidized to Sb (V) by permanganate. Acidity is critical. @lrolyais may occur if too Ilttle acid is present while stiong acid KIves high results due to oxidationof chloride. Wil@d
have

and yoq#

titrated Sb (III)

in HC1 with eerie sulfate with iodinemonochldride out at 50C. using fmoin
15 ml. Of concentrated HC1

as catalyst. The titration is c-led Indicatmr. The solution

should contain

per 100 ml. of solution. T3tratlonwith dlchromatehas alsu been r-tdgl, - howevw, the method 1s unattractivebecause 2 to 3 hours

me reqtied for the oxidation and the endpoint is not very shw. Antimony(V)has been determinedby titration with titanoua ,., .9uJfate92.After oxidation,with brorhine, the solution is boiled to remove excess mddemt. The titratibn is made in an inert atmosphere

(i.e. C02) above 600C. using indigo carmine indicator. This approach does mt seem practical for a redlochemicalyield determination.

Because antinxmy is easily lost by Volatilizationfrcua hydrochloric acid media, dlssoluttonwith this reagent should be carried out under total reflux. Dissoltiionulth sulfuric acid and a reducing agent or an alkall fusion prevents the loss uf antimony and is preferred. The metal is soluble in hot sulfuric acid. Bisulfite fusion in a porcelain or si~ca crucible dissolvesthe metal and lead aJJ.oy. The cooled melt is soluble in a dilute hydrochloric- sulfuric acid media. The Sb(Ill) sulfide is soluble in hot stiuric acid; the Sb(V) *
27

sulfide in alkall auHate solution

. B~OUS

containing

free

.wlfur

or

in

acid. Fusionmethcds =e recommendedfor samples containingoxidized

material that may not readily dissolve with sulfuric acid. Scdium hydroxide in an iron crucible, dehydrated sodium thiostiate, and a mixture of sodium carbonate and sulfur in a porcelain crucible are used.

VII, COUNTING ~Q&3

The common fiaEion ~cduct eatimony i80topee encounteredin analysis ue

and b. 6 hr.

2.4y Sb125, &

SblB

126 Sb , and 93 hr. SbW.

&megbr.

sb

126

cooled material. Of these may be observed in shoi-t

126 which is a pure isotopes, all may be gamma counted except the Z@d Sb beta emitter. Gross beta or gamma counting can be cbnfusing due to the grw in of the tellurium daughter prcducts. Gamma counting using a gamma spectra are analyzm is recommended. Characteristic

mltichermd

104 given by Heath and Crouthmlello5.

VIII. COLLECTEDRADIOCHEMICALPROCEDURES FOR ANTIMONY In preparationof this monograph the author requested from the other mnograph authors radiochemicalmethods for antimxiy uEed in their lakarat wf.es. These methcds are included in the fdlcwing compilation which is belleved to be representative of the methnds now in use.

28

PROCEDURE 1 (ION-EXmGE)

Note: This procedure has been used to obtain pure Sb i%actions from U, Th, and Cf fission pmsduct mixtures but should be applicableto almost apprcodmately&@ end

my mixture of actlvitiem. Chemical yields me

it usually takes about five hours to run four samples. (W. E. N.) ----1. -------------------------

Add 30 mg Sb curler plus 1 mg Mo, Te, Sn carriers. (&lutiQn at

this point should be free of oxhiizing agents----ifit is not, pp~ Sb with pH 6-7 acetate buffer, wash once with dilute acetate buffer, dissolve in 8 ml ~ 2. Ad@t to ~ H@. HC1 (25-30ml vol) - . cool - add 10 ml &C> ice

(oxsorbent, made by Burrell Corp.) - digest cold 5min. - bubble in 02 1 min. - cent - wash twice with H@. filter it, waah with H#,
3. Mssolve

(If Sb does not centril%&e,

and dissolve It off the filter as in Step 3). each of Sn

sb in 4 ml cone. HC1 + Mquid Br2 -mid 1 w

and MO carrier - add NH@H.HCl to reduce Br2 - dilute to 30 ml - add 1 ml~NaI 4. Add ~ - digest hot 15 min. ~ NHkFoHl? Ice cool - saturatewith H# - digest hot

15 min. (no longer) (saturatewith H@

tith (~ HCl + H# + dilute KQF. HF).

every 5 min.) - cent - wash once

5.

a) Dissolve Sb#3 in 15 ml hot @

HC1 - add 1 mg Te - pass in E&

cent.
b) Addling A.e+3 - digest -

filter Aa#33.
c~j

6.

a) Adsorb ~

on _

A-1 anion exchange column (6 mu x 10

Ik.wex lx 8, 50-10 Qmesh,pre-equilibrated ulth ~HCl). b) Wash colmn with 5 ml @ 15 ml ~ 10 ml ~ HC1 HC1 H#04

29

PROCEDURE 1 (Ccmtimed)
c)

Elute Sb with 2 ml H@ 15 ml lmillng ~ i%OH

7.

Ad@t

to ~

in HC1 - filter (WhatmanNo. 44 paper) - ice cool -

add 10 ml CrC12 - digest cold 10 min. - pass in 02 1 min. - cent - wa~h twice with O.% HC1, once with acetone, dry at lJ.O weigh aa Sb. -

PRCCEDURE 2 (BRQIIDEDIsTIIL!KCIm) J. W. &neB95

1. Intpduction Antimony is separated fram moBt of the fia~ion products by distillation of the ,trilnmmlde fr~ acid solution. Among the substanceswhich

also appear in the dlstildat are vcd.at compounds (probablythe broe lie mides) of germanium, arsenic (III),tellurium, and tin(n).

Tin(IV), the main contaminantof the distillateunder the conditions is . . .

CmIploti.

Oermanlumtetrabrouddeboils at a considerablytiwer tenrpera-

ture than anttiny tribromide emd is largely removed by discarding an appropriatelow boilhg fraction. !EbI1s removed by am acid hydrogen sulfide precipitationthe presence of ,fluoride ion, the latter

forming a stable complex with the tin and preventing its precipitation. Remaining germanium, aa welJ. as arsenic and tellurium,which have precipitated akmg with anthony, me seperatedby concentratedhydrochloric

acid extractionof the stiide precipitate. Anthony(III ) Pulfide diSmlvea, whereas the othera are unaffectedby the acid treatment. ht tiny iB finally converted to the metal by reductionwith chramous chloride and is weighed
and

counted in this form. The chemical yield is 70 to

90$.

30

31

~~ PRCmDTJRE 2 (continued) Spray trap

(to

of flt into ground glass joint in flask alxwe)--conaists section of glass hellce~ In a I-6-mm-tube.This Shouyibe

a 2n long

~acketed and heated to preyed conden~ationof SbBr3. The very simple methai of heating used 1s to lead the hot geaes from a ltlsher burner under the 3-neck flask up through a large dlar@ er glass tube to the jacket. The spray trap leads to a condenser.: condenser 125-ml =lenmeyer flask (receivm for distIllat e)--outlet tube from the condenser touches the bottcun the flask of Dropping funnel (fits into ground glass joint in flask above)-see ~cedure for diagram N*t.mk Ground-offElrsch fumnels: Coors 000A (one per eemple) Filter chimneys (one per sample) IYlter flasks (one per sample) lVo.40 Whatmsn filter circles: 7/8 40-ml Comical centrifugetubes: ~ex diameter--weighed
832u (four per sqple)

Filter beaker containing15-ml slntered@ass cmcible of fine pmoslt y (one per sttidizatlon}--see ~lff 100-ml beakers (one P sttidization) Repuation and Standmdization of

&)-ml slntsred glass crucibles: fine porosity (two per sample) WaBh bottle Stirring rods 4. Preparation and Standardizationof Carrier
Dissolve

18.7

gm of SbC13 in F& HCl ami make the sqlutionto a

vulme of 1 liter with the acid. Pipet 5 ml of the above carrier solution into a weighed filter baaker. (This beaker has a 15-ml, fine porosity sinteredg~s crucible

Bealed Into the aide near the top BO that the operationswhich follow-32

PRmEWRE reduction, filtration,drying, ~

one vemel. )

2 (continued) out h be Cezried this

~i---~

Add 5 to lo ml of CrC~

1301utioh (Oxsorbent . After con-~ )

version to Sb metal is complete,filter, ami wash the fiecipitatewith ~ portions of H# end absolute C!H30H. llrythe filter ~~er con-

taining the Sb at 100 for 1 hour. cool and Veigh. . Rrocedure 1. To the sample In a DO-a, 3-neck distilling flask, add the follow1 ml of MO Csmrier; 0.1 = of

ing reegenta: exactly 2 ml. of standard Sb Cmier; 2 mI of sn carrier; 1 to 3 ~ of 85% H3p04J &?r_te=

s (Rote 1); ~ ml of cone. H#4

(slowly). Place a 360 khermometer,

a short spray trqp leading to a condenser,and a dropping funnel (see diagram) in the three ground joints of the flask. Plug held on by spring 7.nml IV2 .ialet

Made from a 25-ml

Pyrex graduate

Rressure type stopcock

Vigreaux points In this to break up the drops of HBr

Dropping Funnel

tip--fits to bottom of flask

2.

Bubble N2 through the solution in the flask while 15 to 2X)ml of

cone. HBr is kided dropwlse from the dropping fu,unel. The temperature
33

PRCXEOUHE 2 (Conthled) of the liquid in the flkek. mdntd,ned at ~ is to 230 (Note 2) W

means 07 a Fisher burner during the 15 to .~ min. required for the addition,ofKE!r, The distillatewhich comes over belxni 180 is discarded end the eddltiom of EC& is begun only aft= a temperatureof 210 is reached (Note 3). 3. To the distillate (180 to 230) in the 125-ml Erlenmeyer receiver and 2 mJ of N~.H@ Make the a few ~OPS

add 1 ml of Te cerrler, 0.5 ml of As C=ier,

(Note. 4]. Neutralizethe solutionwith cone. ~OH. neutral solutlon sllghtly acid @th. cone. HC1 d ~

of aerosol solution md 0..5to 0.7 ml of cope. ET. Saturate with .. H@ u@il the sulfi~eprecipitatebegins to set,tle, leaving a c>ar

supernate. Tbls should be done as rapidly aspossible because SnL.and SnS2 will also precipitateafter a short time; also the precipitation should be cexried out at rooq temperatureor below to aid in the rapid formation and coagulationof Sb2S3. bansf~ the mixture to a 4-ml

conical tube and centrifuge. WaOh the precipitatewith 15 ml of ~

H2SOh containing

aerosol. Discard both the supernateand the washings.

4.

Boil the precipitatewith 2to 4 ml of cone. HC1, dilute to 20 ml Transfer the supernateto another

with H20, and centrifuge (Note 5). 40-ml centrifugetube.

5.
Sn

To the supernate,add a few drops of aerosol solution,0.1 ml of carrier, 1 ml of Te c=ier, &nd 0.5 to 0.7 ml of cone. HF. Pre-

cipitate and wash sulfides as in Step 3. 6. Dissolve the precipitate in 4 ml of co~c. HC1, boil off the H#

formed, amd filter the solutionthrough a 60-ml fine sinteredglass crucible into a b-ml centrifugetu~e.
7.

Add a few drops of aeroEol solution and 0.5 to 0.7 ml.of cone. EF ~.

and precipitateemd wash Sb,#3 as in S&p 8.

Dissolve the precipitate in 5 to 10 ml of cone. HC1 and bail off Make the solution 3 to ,% in HC1 and filter through @ 60-ml
34

the H@.

PRaEDLIRE 2 (Caltinued)
fine alntered glem crucible ixcto a hO-ml centrifuge to tube. precipi-

9.

Add sufficient

CrC12 aolutinn 6tart

(Oxaorbemt) through

cm@.etely

tatamasthemetal.

filtering

a veighed Ho. 40 Who&an

filter chcb,

7/8 dim=,

titw

1 b.

or IW,

UOhg a SOUU&Off
of E#

Elrech flmuel ad
d abeolute

a Chinuley. Wlulhthe metal Vith 5-ml portions

m-y at lw for

CH30E.

15 min.

cool, Veigh, -

mow

(Note 6). Eotea 1. SuMur 10 addEd to tk of Br2 frm m. 2. All t-ature8

3.
Mwh notti are at about

131etim

flaak to FeVent the fozmatim

590 mu of ~

pressure.

of the Ge in the fissionqroduct 801UtiOn is remved vhen

the flaotion cd= k.

5.

m
hydrate AE, or

ti

M
rducee

is al~.
my Sb(V) in the diutillde vith to 6b as Sb(III). Sulfide

~aajne
Any w,

tich

is

prmipitated

along .

is hsdible

in C-.

ECl, uhereaa 6b#13 5s ~oluble

is after 8bm. des~ far

6.
Sbw.

procdame uscri=
is attied with

the

~ermination

of

Comting

4 daya, in vhich
lhe half-lives of $35

time

9.3h Tela
fm *.*. ~ SIW

has

grown into q quilibrium

reelulting Eau-llvet3 @L frail from thermal fart of

obtained abut

neutron neutlwl

fiemion fission

average

(1L Me7 neutrom) is probably the

ewerege dstence

zo

The cauae

this

discrepancy

of another

Sb isotope

having a *er

half-li?e

than 2.7y Sb13.

35

FRaxuum (q
K. F.

3
PRECmZATION)

wymmzmm,
Flynn,

a-om~

n, L. E. GlendeDI and E. P. %teinWg 96

Ill-&duct ion ~s procedme was developed for the radlochemicaldetonation ndxtures. 9auQlea of U=,
@35, em PU239

of S0 in fission @dct

whichhad undergone alnrc &3 ad S#=.

127 fiasione were aualyzed for both Sb

The decay curves of theme iaotope~ ehowed leas thau O.5*

Contamhant
e~nts

of any long M*
factors tlon of fran

to be present.
have

Accurate

decent-nation but a aepar~

specific

not been determined,

corrtai~ A8~ tracer

inactive in

Sb fra

a solution

131muedno

activity of greater

the final Sb saqple, indicating

than 103. Chemical yielde me

a decontamination about

facta

25$ wd the analyalB

cau lm performd h

about 40 minutes or less. Procedme

1.
of vith ~

to the sempI.c (tiee of nitrate) in a dieti~tion

atenderdized s drop the Ueing flov of ~~ m c~i= insure (10 ~ Sb+5/nil) L ml of

flaak

L d ~ii zinc of liquid

6~ ~.
wauulazd

Br2 to into &

exclmnge. ~

Add 5 game of

aud paas braline (i cc/see

20 ml of Btremn to

HCi containing gas

a few drops the

ave?ep the

through

Ey9tem.

rate

for

5 min. ) h@razW-HCl
Centrifuge

2.
boi~ time

Add 10 q

Te d
vith

1 wam
H#.

ta the solution.
and discerd ppt.

Heat is

to zero -

and gas for

(!l%is

Te remval). HHLOE, dilme ~ aud waah. to 30 ml, and gee in ulth H#.

3.

hdd 5 ml of cone.
the 6b~3

Centrifuge

Di8eolve

2 ml cone. ECl, add

1/2 ~am

liaE803, dilute to 10 ml, and boil. Add 3 ml of &hydr~. Eel) azd boil. Add 1 m
@5).

qulnollne (3$ solution in ~

-Ac till

Cone. qm,

pptq is ccmglete
far

Uaah with E@, &LC@Ol,

dry at llOC.

15 min.

36

PBCCEDURE 3 (Continued)
Carrier Standxu-diz.exlon:

Take 5 ml Of Sb canrier solution (in ~. HCl).

Add 1 ml Of 6~ HCli 1/2 gram IVaE303, end boil. Add 4 M. of 8-hydroxyquino~ne (3$ solution
In ~

HC1). Md

1 ml of cone.. NH40H and ~

NH4Ac

until ppt~ la complete (@=5). at llOC. for 15 min.

WaGh with H@,

alcohol, and ether..,ry D

Weigh. tiatietric Factor = 3.8.

PRocEDlJRE4 , ($bH3 VOLMKUZWTON, SHNH!R~

c YIEID)

D. L..We

Rapid Separation

of

Antimony

from

Ileaion Produot l.Hxtures

DecontaminationFactor: Chemical Yield: w Time: 10 seconds

107 for gross fission products

Basis of Method: Formation of SbH3 and its conversionto fi metal Zinc metal (40 mesh) is placed in a distillingflask and mrmed to looc. Auti.mm.y(IIIcmier ) plus fission prcducts plus 30~ H#O~ are

droppd onto the Zn and SbH3 is immediatelyformed before the Zn has had a chance to.convert the Sb(III) to Sb metal. The SbH3 (plus the H2 formed) passes through a CaC12 &ylng tube and then through a heated smaU diameter quartz tube (Pyrex iB acceptablebut ittiesnot keep its shape when warmed with a burner). The Bb~ is convertedto Hb metal, part of which collects as andrror on thecool portion of the quartz tube and the rest @50$) on a fine fritted gl.aSB filter. me metal is If it is dea~able to study the I

rapidly dissolvedwith wsxm H#04.

decay products of.. the metal may be dlsaolvd in tartarlc acid. The Sb, chemical. yield may be determined either by using 6b124 tracer or a spectrophotnmetPic determinat ion of the Sb-rhdamine B complex. Arsenic is expected to follow the antinumy;however, most of it

37

PRmmJRE collect on a dlf ferent B

remved
posit Ion of

4 (continued)
the

tube.

WmSerIic
hypochlorlt the

can be
e. prod~t

from the Sb metal by leaching with

ex-e is obtained even if

sdlum some of

Complete m is Sb(v).

fission

PROCEDURE 5 (Hm41DE Ex!mm!Icm, ml!AL PREclTmATIoH) A. (Rapid separation ~elberg .4nd A.C. Yappas4 enriched Te-128 and Te-130)

of

Sb from

irradiated

Reccsmnenblfor decay scheme studies where yield Is not-@ortant. TYme Ofsep eration: .Iessthen 5 ndnutes lkcont audnat ion: 5 x 104 for Te lo5 fm Sn

m-lCKI for I chemical Yield: @-y@.. . ~ 1. Isopropyl eIJheT washed repeatedlywith 8 solutdonof FeS04 and tistl~ed fram solid FeS04 and lkOH and equlMbrated ulth
2. Antimony carrier 10 W/ml as

SbC13 in ~

HC1. Before use, it i13

OXidiZed by shaking with 2 drop6 l!m2 in 10 ml

benzene and vashed

3. 8n~12 Sblutiun

tith

10 ml benzene. HC1.. The solution

- ~

mg/ml Sn as SnC12 in ~
be fkeeh when W.

should

4.

Cr*

Solution.

&C13

mlution,

UJ in T321, reduced by is
granulated metalllc Zn.

boiling with

emalgemated,

5. HC1 - Cone. and q

6. IUI03 - Cone.

36

PmmmRE 7. 8. 9. Hr2 Henzene N@Ik.H@, 50$

5 (Conthled)

S@E!s!k 1.
2.

W-ml. beaker
GhBS

rmi

3. Sintered glass gooch crucible 4. 5. 100-ml suction flask 50-- mwratow

funueli

Rrocedme: 1.

Dissolve the target in 5 ml .% HC1 to which is added 2 DW ,Sb(V), ,,

Add under . After about with vigorom sttrrlng filt~ 2.5 ml SnC~ with solution through per 100 mg

Cerrier. target

1/2 mintie, 2 ml. 91JRC1.

sucti,gn

a gooch,

and wash twice

2. Wansfer

the filtrate ta a aeparatbryfunnel containing 10 m

C6H6,

1.0 ml. isopropyl ether and 0.1 ml Er2 per I.00 target. Shake, mg the funnel for ataut 10 sec. (Riatinctbrown color of E?2 should remain in

the organic prose,, showing complete oxidation) Discsrd the water phase . end wash with 1 ml ~ HC1. phase to a se~atory funqel containing 5 ml

3. Transfer the org~c

9~ HCl and 1.0 ml SnC12 solution and shake, (The organic phase show be colorless after extraction,shcndng cmplete reduction). 4. Tremfer the water phase to a sepxratoryfunmSl contacting 10 ml of

C6H6, 1.0 ml isopropyl ether and 0.05 ml Erp (or as Ilttle 8s possible) and shake for 10 sec. (~ent and wash with 1 ml . HC1. 9N 5. Transfer the oregnic ph~e to a eepexatcmyfunnel containing 5 ml
9X HCl and add dropuise

WOWI

CO-)..

Discard the water phase

a mlnlmum amount of SnC~ solution (O. to 1.0 u). 5

Shake,,eventualJy add SnCl tu just discolor the,organic phase. Tbls solution

can either be used for liquld beta counting; or:

39

PROCEDURE { Continued) 5 6. Add 2-3 mg SbC13 cexrier, heat the soltiion,and add approximately

15 ml balling hot ti++ solution. Filter the ~olution and wa8h the precipitatecerefully in boillng hot ~ HC1, then with ~OJ alcohol and

ether. (SamemetalJlc Sn is also pptd.)

mocmmm

(SUIKCDEFRECTPITA!LCON) A. S. Newton and W. R. McDoneIl

Element Seperated: Anthony Parent Materiti: Tln Milking fiocedime (Sb froh low energy p, d, or n produced Sn activity fractions) Yield: 60-80$ De~ee Of purification: Atlead a factor of 104 from Sn Procedure: 1. Tuna 3-4~HCl solution of the Snti 10 ~ Sbcarrier (Note 1). ppt,

Add ticm powder to excess (hydrogenevolution),heatwith sttiin& &metal

(black)i ~lter byv&nnun thrbugb a sinteredglaea filtering

crucible.
2. Dissolve the Sb in ~saolve stirring). eq~ r~ia, dilute to ~ the

acid, WSB in H2S & s~ with concentrated

pPt.S@3

+ s. md

the sdfide

out of

HC1 (wersdng

3; ~d
pass

,. 10 mg Sn+4 cexrier ttifiltrate; Heat in boillng nte~ bath,

in E2S to saturate,ppt,orange Sb.#3. Centril%gehot, decemt. in concentratedHC1. Dilute to ~HCl.

Jtwice.

Dissolve Sb S 23 4. Repeat Stq

5.

,,
Filter the Sb2S3on filter paper and waah wi~h water. Eeat gently

(Note 2). 40

mxmmm Notes:

6 (Continued)

may be scavengedout of this &lXing %y &ing 10 mg In c=rier 1. Iridium ,. to initial Sn solution (Step 1), repeating the Fe reduction if the amount s of In activity present Waxrant it.
2. The suMide should not be relied upon for accurate yield determination.

PROCEDURE i (smIDEmmImsomc PRECIPITATION)

% H. L. Finston (Separationof Sb from Sn) 1. Dissolve the Sn in 1+8$ plus a few drops of EIt03 HF and evaporate the of Sb carrier
into and dilute the solution

solutionto about 1 ml. Add 1 ~

to .20 ml and bubble hydrogen s~ide

each solution for 5

minutes.
2.

Centrifugeemd dissolve the precipitatein concentratedHNO 3. 10 mg of Sri++. c-rier and evaporatethe solution neexly to dryness. dilute the solution *Q
20 ml. Add

3. Add 2 ml. of HN03 d

3 drops of

concentratedHC1 and heat the solution to neer boiling. 4. 5. 6. 7. Add with stirring,4 ml of phenylsxsonicacid. Centrifugeand discard ppt. Bubble E@ into the mpernate to sgainppt,the Sb. .,

Filter, mount, and count.

41

mx!mum (AKTIMONY,-ON ACI!IVATTON-IS

8 (I-C CARRIER)-D)

G. W. LeddlcotteU9

SCOPE This method of neutron activation snelyais can be used to determine microgram and submicrogramamounts of anthony in a variety of materials. Under the conditions of neutron tiadiation that =e apecifled,the x10 -7 ~.

lhit of measurement of the method 16 almut 1 x 10-8 orl

The Sensitivitymay be depending qpon which nuclear reaction is u6-. ,.. neutron fluk. increasedby the use of a hlgheir PRImImE Antimw by can be dete&nined quarititatively measuring the radlo& gb=3, by the sloi

actitit induced Irito stable 1sotopes, Sblti y its ne&on reactioni, Sbl=(n, 7)S#2

and SbW3(n, 7)Sb124. The isotopic

activationcross sections of these reactkrie are 6.8 ~ 1.5 and 2.5 ~ 0.5 barns, respectively. Anthcmy-121 is 57.25* abundant; Sbw has a half

Ilfe of 60 d.and emits both beta and gamma radiations in Its decay. Other products of these neutron re&tions, i.e., Sb-(3. gb124ti(l.3m), tlon describedherein. ,,
Test portions of the test sample and of a comp~ator swipie (in the

5 m),

~ @l.m2 m), will not Interfere inthedetermina(21

this case, antimony metal) exe Irradiated ORNL reactors

portions antimony are

slmultaneouely

In one of

.. . for an appropriatelength of tinie The i&dlated j

dissQlved, is and a known amount of added to each as inactive ant tiny;

test
as

chloride,

a c~ierll

fcrr the ~adioactlve

antImony. Holdbeck (scavenging) carriers,which are arsenic, tin, copper, iron, sodium, end cobalt in solution, are also sdded to the solutions of the teat partions in order to decontaminatethe Sb122 (and/orSbW4) radloactltityilrom contaminantradioactive species in the samples. The ersenic end tin carriers =e 42 seyaratedby distillation.

The antlmo~ cexrier

end the

antimony

radio~tititles are precipitated

as emtinmny trisulfld~l.~@3>

in order ti renmve them from the other Additionalmxqfenging stepsare

holdb.ack. c.sqi.ers and radoelements.

used to further decontaminatethe antimony trisulfide. As an alternateprocedure to the precipitation of antimony trisfiide, the antimony can be convezrbed o antWbhy metal by reduction t with chrcmwus chloride. The ant-my trisulfide,u the antimonymetal

is weighed ahd is *hen asaayed for either beta or gemmk rmiioactivity. The quamt$tyof antimony in the original semple ik obtained by corqmring the 9bU2 Sbl@ &ed
S!lYmJs , T@
.Iaboratory methd tu w develop@ .@cimony @ is USed in the QFUtL Ihiclear Analyses

(and/orSbl.24) radioactivityfound in the test sample with the radioactivityin the e@nparator sample that WE@

(and/or#4.)

in.the same manner 8s the test sampti.

determine

in metals

and alloys.

It.can be
mmunta

adapted for the determination of microgram and Suhmlcrogmm

of

smthony la @her materials. For the procedure which uses the Sbm (n,y )Sbm rea@ion, the

Mmit of measurement is about 1 .xlo-8 g; this quantity is the smallest . . weight of anttiny that cam bq determined quantitatively when the test
prtion

is fiadiated at a neutron flux of 5.0 x 10U neuGrons/cm2/see, 123(n,7 The Lboit of measurement by the.Sb. tin )Sb reaction,

f~

62 b.

for which a one-week irradiation at the same nmxtron flux is used, la , almut 1.0 x 10-7 g. These lhits & measurementcan be extended downwsxd by the use of higher neutron flux. The choice of the neutron reaction to be used is governed by the the available for the analysis

and by the nature of tie test sample. hewn interferencescau result if the sample contai& iodine as 1~
neutron reaction (n,a) orIIm

tin as S#4.

!Chefasttie ~low-neutron

produces Sb124 (60 d).

reactiom on SnU4 till produce SbM5

(2.7 y); the reaction is Snwk(n, Y)

43

PROCEDURE 8 (Continued) SUW5 ~~ S1+5 (2.7 y). If &33 or #35

of ant tiny

is preaeti in a sample,
& the T@oduced necessity of of the the by fiaaicm. of con-

a number of radioactive
The use trolJlng in the of

Isot opea

will

the .ccssperator such factors duration of

ample

eliminates flux,

rigidly reactor,

as neutron irradiation,

position

sample radiohas of been the

and efficiency s~psration adequate

act iv-it y measurements. shown to be reproducible, ant tiny frcm other.

The radiochemical and it ive gives

procedure

decontaminate ion a~le. It

rmiioact

component a in the

iS

advisable to scavenge at least twice for contmsinantradioelements. The chemical yield should be at least 70~ of the added inactive antimony c-ier; a recovery of less than 50$ 10 regarded aB unsatisfactoryand

requires that the analyses be repeated. It iB assumed that negMgible

mmnts of sulfur and mtimony pent =uMidej n@5) =e f med in the

final precipitationstep in which the sntimny carrier arii radioactive antimony &-e precipitatedas antimony trisulfide. SAMPITNG ,.,

If the sample is a solid, weigh out to the newest O .COl g, a m test portion that weighs o.1o to o.. g; if the sempie is a liquid, In use a 5- to 25-ti pofiitin. etih instance,prepare at least du@lsample usespectrogram . cate portions i%r mslysiti As a ctaupsrtitor
icaUy

pure antimonymetal; weigh out to thenearest 0.0001 g dupllcate These suggested sizes of

test portions thht veigh 0.025 to 0.030 g.

the test portions are those arbitr=ily establishedfor use by the CEWiL Nuclear Analyses Gro@ and exe umalJ.y governed by the type of container and the facilitiesused for the irradiation. PROCEDURE Make Ml analpes for antimony on at least dqpllcateportions of

the teat and cooperatorsamples.

44

PROCEDUFW 8 (Catinued) A. 1.
Preparation of Test hrtions for Irradiation

Weigh out ted porticmw of the comparator sample and of instructedin:S~ll~ above.

the teat sample ~

2.

~tioppered, Place te8t portione of eolid materla10 in cork.

quartz tubes or wrap them in alunlnti foil. 3. Place portionB of liquid samples in polyethylenebottles equipped with polyethylenecaps (sealedquartz smpoules may be subatitutad for the polyethyleneImttles). B. 1. Irradis.tion,of Test Portions

Irradiate comparatorand test samples stiultaneously

under identicalconditions. c. &epmation of Irradlatec Test PortLons for halyeia

1. By whichever of the followingproceduceg applie8, Prepme the portions for =alyais: a. Anthmy CanpsratorSample

(1) Quantitatively transfer theirradiatedteet portionof the comparator sample from the quextz tube or alminum wr@ to a 50-ml

volumetric flask. Mssolve the test portion In a small> measured volume of aqua regia; then dilute the solution to 50 ml with water. Mix the solutionwell by shaking it carefuIly. (2) Bymeaus of a volumetricpipet, pipet a l.00-ml aliqubt of this solution into a second 50-ml volumetric flask; then dilute the allquot to 50 ml with distilled water. (3) -e the solmonttiro@QJ then pipet a 1.03-ml

allquot of It -to a 100-ml distillationflask. By means of a volumetric pipet, add to the same distillationflask 2.00 ml of a standsxd carriw solution of & antimony concentrationand 1 ml each of holdback carrier

solutionsof the ions of arsenic, cobalt, copper, Iron, scdium, strontium, and tin (lVote a). Eva~ratethe solutionto a volu@ of approximately3 ml. Continue with Part D below.

45

PRUXDURE 8 ( ~tinued) C b., Solld Test semples (1) If the sample Is a met+, or alloy, quantitatively transfer the -adiated test portion from the quertz tube or aluminum

wrap to a 103-ml distillationflaBk, and then add, by means of a volumetricpipet, to the same +istil&tion flask 2.00 ml ofa standazfi:

c~i.er solution of known sntlmopy concentration. Also mid 1 ml each of hddback ~iers of arsenic, aobalt, copper> iron> s@iuJ str~nti~;

and tin (Note a). To this mkture, mid dropwise enough concentrated mineral acid to completelydissolvethe sample. Evaporatethe solution to a volume of approximately3.ml. Continue yith Part D below. c. LLquld Test samples

(1). Pipqt amallquot of the irra@iatedportlon into a 100-ml distillationflask., By meansof .svolumetricpipet, mid to the same distillationflask 2.00 ml of a standard carrier solution of lmown antimony concentration .a@also @d,l gl each of holdback csrriers of

arsenic, cobalt, copper, iron, sodium,stronti~, and tti (N@e a). Evaporate the solutionto:a volume of approximately3 ml; ,thenenntinue with Part D belOW. . .

D. RadiochemicalSeparationof Antlmon~ 1. To the m~ure of cone. HC1 and 3ntLof ~. ,2. Attach a tiater-cooled ondenserto the distillation c flask. Place the dellvmy tube of the condenser in a distillate collectionvessel khat is set in M ice bath. Bymeans of a hose, in thedistilJ-ation. flask,.@ 2 ml

apply a gentle stream of ah to the flask in order to minimize bumping. .3. llistillthembrt~e in the flask untilthe temper,at~e of the ndxture reaches 11O*C. @ until o@.y approxbnatily5 ml of the

.901ution remains in the flask. Add an additional 3-ti

distillation flask, and then continue the distillation

46

PRamKlm appro-tely
4.

8 (continued)

5 ml of the solutionremains. ,,
DiHcerd the di.stildate and quantitatively transfer the centrlf%ge tube. kia25ti

contents of the distillation flaskto a@-ml of a 8aturkted sOlution of OXSMC

acid; then heat tie mitiure to bear

Ix)illxlg Saturate the solutionwith H@ .

in order to precipitant the e Centrifugethe ndxture ,. . of 2 & :

antimonyaBaritho~ tristiide, Sb@3. discard thesupernatantliquid.

5. Dlstiolve the fi.#3 by mrmihg it ii a Wure of cotic. HC1 &d 2 dropsof conc. HN03. ~

1 ml e=h of holdba& .

cexrier SQIUtiO~ of iron, Cdpp~, strcint iwh, ezui130dium; ~ecipitate . . . sb#!3 by _ 10 ml of COilcHt?03and then boiling the Solutiori. . Centrifugethe mi&ture ahd disc~d the Bup&nakant llquid. Wa6h the precipitatewith three10-ml portionb of hot, cone. HN03. After each @ washing,: centrifuge the mitiure and discard the supa%ataut l&i&. 6. Dissolk the Sb93 precipitatein2ml of cone.HC1.

Add to the solution 30 ml of a saturated solution ofoxalic &id and 1 ml of tin holdback, carrier solution. Heat the ~lutiog to bbillng (the boiling helps to coagulatethe precipitate);then precipitate Sb#3 by saturathg the solutionwith H2S. 7.
that

..

Filter off the Sb#3 through a tared filter paper

is held in a Hirsch, funnel; wash the precipitateonce with 3- to ethyl alcohol, CS2, and ethyl ether in that

5-ml yortions each of ~0,

order. Dry the precipitatefor one minute. Weigh the Sb#3 precipitate and filter paper on an analyticalbalance. Mount the precipitate and count its activity.

47

IX. NEU2RON ACTTVATTOH~IS la n/cm 2/see. the theoretical , With B thermal ReutIOn fln of ~x 10 ,. aensititityof this technique for antimony is reported based on *.M SbW and 0.03 w based on @
106

as 0.CX34ug

124 .ftm en induced m

actltity of @d/a at aatwation.

Because of the lung irradiationttie

magnlttie getiter.

the other hand? an dV8.UtESe Of a re~tive~

10=

lived ,=tivit to decay. Gamma spectra of neutron activation isotopes y are given by Heath
104 , Crouthamel

105 @ ,

BroQlst3bank ~.

For spectra

that cannot be resolved due to other actlvitieathe methods described in Secticm VIII -e recommendedfor chemic~ aep~ati~.
8 V! Table 2 La a partial Ilst of material; tiich ~ve for antimony by thezmalneutron activation WBiS. ken -*

A typical method ,

is described in Procedure 8, section VIII. TABLE II. ACIICVA~ONANALYSIB OF ARKCMORY

!i!!=!E
zro~ Al 61

Remarks
sens. 0.5 ppm

Reference I-08
109, U3

sens. 1 x 104 f=sxlolp

ppm

llo 111

Ge Iiquid Metah BiologicalMaterials Pb

M3

sens. 10-5 ppul f= 3 x 101= 1 x 10-3 ppm

log,

115

112 114
U6

IJ7 0.04 ppm determined IJO

Water

48

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