—.

;. ,_

‘-

8-+ational Academy of Sciences I National m NUCLEAR SCIENCE Research Council

v
SERIES

The

Radiochemistry Elements

of the Transcurium

COMM

TTEE ON NUCLEAR SCIENCE
ROBLEY D. EVANS,
~iC~ Chuinnai

L. F. CURTIl%3, Chairman National Bureau of Standards

Maasachueeth

Inetitute of Techuolo~

J. A. DeJUREN, Secre*y Westlnghouee Electric Corporation C. J. BORKOWSKI Oak Ridge National laboratory ROBERT G. COCERAN Texas Agricultural and Mechanical College SAMUEL California EPSTELN Inetltute of Technology J. W. IRVINE, JR. Mammchueette InBtitute of Technology E. D. KLEMA Northwestern W. WAYNE Univerai@ University

MEINICE of Michtgao

J. J. NICKSON Memorial Hoepital, New York

U. FANO National Bureau of Standarde HERBERT Nwlear America GOLDSTEIN Corporation of

ROBERT L. PLATZMAN Laboratoire de Cbimie Physique D. M. VAN PATTER Bhrtal Research Foundation

Development

LIAISON
PAUL C. AEBERSOLD Atomtc Ene~ Commission J. HOWARD MoMILLEN National Scienoe Foundation

MEMBERS
CHARLES K. REED

U. S. Air Force WILLIAM E. WRIGHT

Office of Naval Reseamh

SUBCOMMlllEE
W. WAYNE Untvereity MEINKE, of Mlchlgan Chairman

ON RADIOCHEMISTRY
HAROLD KIRBY Mound Labomtory GEORGE LEDDICOTTE

GREGORY R. CHOPPIN Florida State University GEORGE A. COWAN Scientific Laboratory

Oak Ridge National LalMmtory JULIAN NIZLSEN Hanfonl Laboratories ELLIS P. STEINBERG Argonne National Laboratory PETER C. STEVENSON of California (Livermore)

Los Alamos

ARTHUR W. FAIRHALL I@vez73ity of Washington JEROME HUDIS Brookhaven National Laboratory EARL HYDE Univerai@ of California

University

(Berkeley)

LEO YAFFE McGU1 University

CONSULTANTS
NATHAN H&LOU Naval Radiological Defenee Laboratory JAMES DeVOE University of MicMgan

WILLLAM MARLOW National Bureau of Standards

CHEMISTRY

The Radiochemistry of the Transcurium Elements

G. H. HIGGINS

Lawvence Radiation Laboratory University of California Live~move, Califo~nia

October

25, 1960

LIBRARES PROPERTY

Subcommittee National Academy

on Radiochemistry —National Research Council

of Sciences

Printed in USA. Price $0.50. Available from the Office of Technical Services, Department of Commerce, Washington 25, D. C.

FOREWORD
The Subcommittee on Radlochemlstry Is one of a number of subcommittees working under the Committee on Nuclear Science wlthln the National Academy of Sciences - National Research council . Its members represent government, industrial, and university laboratories In the areas of nuclear chemistry end analytical chemistg”

The Subcommittee has concerned Itself with those areas of nuclear science which Involve the chemist, such as the collection and distribution of radlochemlcal procedures, the establishment of specifications for radlochemlcal.ly pure reagents, availability of cyclotron time for service irradlatlons, the place of radiochemistry h the undergraduate college program, etc .

This series of monographs has grown out of the need for up-to-date compilations of radlochemical Information and procedures. The Subcommittee has endeavored to present a series which will be of maximum use to the working sclentlst and which contains the latest available Information. Each monograph collects In one volume the pertinent information required for radlochemical work with an individual element or a group of closely related elements.

An expert In the radlochemlstry of the particular has written the monograph, following a standard format by the Subcommittee. The Atomic ”Energy Commlsslon has the printing of the series.

element developed sponsored

The Subcommittee Is confident these publications useful not only to the radlochemlst but also to the worker In other fields such as physics, biochemistry who wishes to use radlochemlcal techniques to solve problem.

will be research or medlctie a speclflc

l!. Wayne Melnke, chairman on Radlochemlstry Subcommittee

iii

INTRODUCTION
This volume which deals with the radiochemistry of the transcurlum elements Is one of a series of monographs on radlochemistry of the elements. There is Included a review of the nuclear and chemical fe,atures of particular interest to the a discussion of problems of dissolution of a radiochemlst, sample and counting techniques, and finally, a collection of radlochemlcal procedures for ‘the element as found In the literature. The series of monographs will cover all elements for which radiochemical procedures are pertinent. Plans Include revlslon 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 the transcurlum elements which might be included in a revised version of the monograph.

iv

CONTENTS
I. II.
General Comments Reviews . . . of . . . 2 . . 1

General
the

of the Chemistry Elements

Transcurium

III.

Table

of Isotopes

of the , . . Element
5

Transcurium IV. Review
Chemistry A.

Elements

.

3

of Features
Most

of Transcurium

Interesting and Chemistry and .

to Radiochemists

Coprecipit.ation Precipitation

,

.

5

B.

Complex Chelate

Ions

Formations Behatior Chemistry of the

.

.

6 . 6 8

c. D.

Extraction Ion Exchange 1.

.

.

Separations actinide

e and lanthanide

a

.

8

2.

Separations elements

of the trana curium from each other . 14

v.

Dissolution Problems Transcurium

of Samples Related

and Special the . . 18

to Handling . and . Procedures

Elements

~.

Counting Source

Procedures Preparations Separation

.

. .

20 23

VII.

Specific

v

The Radiochemistry

of the Transcurium
G. EL HIGGINS

Elements

Lawrence

Radiation

Laboratory

University Livermore,

of California California

I.

GENERAL The

COMMENTS element group is composed of berkelium (Bk), atomic

transcurium

number fermium (No),

97; californium
(Fro), number

(Cf),
100;

number

98; einsteinium
(Md),

(EH ), number
101;

99;

mendelevium

number

and nobelium

number

102. elements are all synthetic; or charged Their that is, particle discovery they are all usually reactions on isotopes

:. produced of ele -

These
by multiple

neutron capture

ments of lower
by Thompson.,l they shell of the etist the Ce+3 compose is being

atomic number.
With the the inclusion half

and production

is described
103

of the as

yet undiscovered series in which

element the

second

of the actinide chemistry Excepting

5f electron to that they to of

completed. or rare

Their earths. ions

is extraordinarily Bk (and possibly

similar No),

lanthanides solely +4 state

as tripositive under (=1.6

in aqueous equivalent

solutions. to those

Bk can be oxidized required for otidation

condition v). properties

to Ce w The

chemical rest,

of any

one

of these to speak

elements of many

are

quite

similar

to those properties be divided

of the

so it is appropriate terms. parts: The

of their can

chemical usually

in collective into three

radiochemical

procedures

1

1. 2. 3, The that and

The

isolation

of a tripositive of the tripositive of the actinides actinides

lanthanide actinides from each

-actinide from other.

fraction.

Separation Separation transcurium Pb-Bi

the lanthanides.

have

characteristic with

a decay some

energies

(note nuclides) they fission

the light short

isotopes fission

may

be confused .

transcurium properties from

spontaneous

half-lives without

Because entirely

of these

can be identified products

and measured some

being

separated for

, and hence . lightest

of the procedures

do not provide

complete

purifications The the last

transcurium occurring several

element, natural

Bk,

is five

atomic

numbers

beyond

abundantly of Bk are produced

element, more several

uranium. than 238,

The

longer-lived this most

isotopes easily away

mass

numbers is

so even

transcurium occurrence. in larger have

element

transmutation elements have

generations not yet been and

from

natural for study

Therefore than microgram

these

available Thompson positive from

quantities.

C unningham2

and Muga3 Bk and Cf ions 5300

reported

the magnetic solution

susceptibilities spectra although

of the tri in the range Cf +3

as well

as the

absorption colored

about

to 8700A. absorption they

Neither peaks

ion is at 7800

strongly and

displays remarkable and Cf. almost

two weak in that No such

8300A.

These

studies

are of Bk

were

performed possible

on submicrogram on Es, levels, Fm, Md, have

quantities or No, been

work. has studies,

been

and in fact on Md It is what

no chemical

even

at tracer

possible

and No because clear that there from .

the half-lives is very tracer little studies

of the observed information

isotopes these with

are

so short. except

about

elements

is derived lanthanides

and comparisons

the chemistry

of the

11.

GENERAL ELEMENTS General

REVIEWS

OF

THE

CHEMISTRY

OF

THE

TRANSCURHJM

reviews

of the books

chemistry and articles:

of the transcurium

elements

can be

found

in the following

2

G. Publishing

T.

Seaborg,

llThe Tran~Urani Mass.

Um Elements,

II Ad&~On.We~leY

Co. , Inc. , Reading, Katz and G.
, Ltd.

, 1958. [Ref. 4. ]
I!chemistry [Ref. G. R. 5. ] Choppin, and G. T. Seaborg, of the Actinide Elements, “

J. K.
Methuen S. J. Am.

T. Seaborg,
1957.

and Co. G.

, London, B. G.

Thompson, Sot.

Harvey,

Chem.

76, 6229 (1954). — J. Chem.
Louis

[Ref.6. Educ.
Muga, “ Proc. ---.-,

] 1959). [Ref. 2. ]
and Peaceful

B. B. S. G.
Research

Cunningham, Thompson

36 — (January,
!lMethoda U. N. —,-----

and M.

of Production Intern. .-. Con-f.

on Transcurium Energy, 2nd,

Elements, Geneva,

Uses

Atomic

III.

TABLE

OF

ISOTOPES ‘1/2

OF

THE

TRANSCURIUM Mode

ELEMENTS of Decay

Nuclide 97Bk 243

4.5h 4.4h 4.98 1.8d =10 4 y d

EC, EC, EC, EC
a

99+ L70; a,
99 +~a; a,

O. 15% 6X 10-37,

Bk244 Bk245 246 Bk Bk247

99 +~.; a, O. 11~’

Bk248 Bk249 Bk250

16 h 314d 3.13h

$-, ~-,

70L7.; EC, 99+%;

30~’

a 2.2x10-370;

SF,

6X10 -6~O.

Pa EC,
h

98CP4 cf245 cf246 cf247 cf248

25 m 44 m 35.7 2.5h 350 d

7070; a, 307”
2X 10-4%

a; SF, EC a; SF>l a; SF,

.5X10 4X 10-4~0
15%

-270

98cf249 cF50
cf251 cf252

360 y
10.9 CIS 800 2.2y y y

a; S“F-O.
a

a,

9’770;

SF,

3~0

3

111.

TABLE

OF

ISOTOPES

OF

THE

TRANSCURIUM Mode

ELEMENTS of Decav

(Contd. )

Nuclide ~f253

M_
17 d { / 56d

E~246 99 ES247 E~248

7,3m

a,

EC

a 25 m 2h 8h 1.5d =140d 20.03 480 37 h 24 d Ehort d d EC, EC, EC EC, a a; SF, a; no ~~-, P1399+7’0; EC =0. 17, 8X10-670 99 +7,; a, 0.53~0
99+~o; a,

0.3~o O. ls~o

E~249
~B250 EB251 E~252

99 +~,;

a,

~ooFm

248

0.6m 150 B 30 m 7h 22.7h =3.0 3.24h 21.5h 3-4h d

a

Fm249 Frn2’0 Fm25’ Fm252 Frn2’3 ,ooFm 254

a

a,

EC
a =170

EC -9970;
a;

SF < 4X10-2~0 897.; 5.50
a, 117.

EC,
a;

SF,

X10-2~0

Fm2’5 Frn256

a; SF

< 4. 5X 10-3~’

SF = 100~o

— Md256 =30 m

a+?

EC

102N”253

=10s

a+?

4

HI.

TABLE

OF

ISOTOPES

OF

THE

TRANSCURIUM

ELEMENTS

(Contd,

)

Nuclide N0254

k 1

Mode

of Decay

38

a+?

~~3—

256 (tentative identification)

0.25

s

a+?

Abbreviations a = seconds, EC = electron SF

in the table m = minutes, capture,

above

are

as follows: d = days, emission, y = yearm,

h = hour~,

a . a particle fission

p- = negatron

emission,

= spontaneous

decay.

A more the compilation Physics, decay Vol. schemes,

complete

description

of most

of these

nuclides

can be found

in

by Strominger, 30, No. 2, Part

Hollander, II, pp.

and Seaborg The tabulated.

in Reviews a particle

of Modern energies,

585-904. are

and genetic

relationship

IV.

REVIEW
MOST

OF FEATURES

OF TRANSCURIUM

ELEMENT

CHEMISTRY

INTERESTING

TO RADIOCHEMISTS

IV. A.

Coprecipitation The tripositive that one during

and Precipitation actinides latter display (usually steps. from lM ),

Chemistry such Ce marked or all La) form similarity is ordinarily insoluble acids to the used lanas a from

thanides carrier strong

of the

precipitation

They Less

fluorides

( ==3-5M— ) acid, acidic

oxalates ( *O.

strong

(x 1-2M ), — or hydrated in dilute

phosphates ofides in

in slightly basic

solutions These diesolve

and hydroxides are insoluble

solutions. readily

hydrated in excess such

oxides (40%)

carbonates, complet-

but they

carbonate

or many

of the

ing anions WhiLe oxyfluorides from

of organic there are

acids

as

citrate, ions which coprecipitate as insoluble of fluorides lanearth

several acid

other

at lower or

concentrations, unique Ly carries

the precipitation Sc +3 , Y +3 ,

=3M— HC1

HN03

the tripositive The alkaline

thanides

and actinides,

thorium,

and the alkaline

earths.

5

group tated

is

left

in solution oxides

when from

the

remainder -free any

of these

elements

are

precipiSr ++

as hydrated

carbonate with

solutions.

Holdback step.

enhances

the separation

achieved

single do not or silver

precipitation carry

Of course, sulfides, lead

the transcurium chromate, barium with

elements sulfate, zirconium 7

appreciably

on acid

chloride. zirconium iodate and

Bk+4 eerie iodate,

coprecipitates and insoluble

phosphate,

hydroxides.

IV. B.

Complex The order > nitrate > sulfate

Ions

and Chelate

Formations power for of different anions anions, is fluoride and carbonate formation +3 ions are for and and > > is so

of the completing > per chlorate for dinegative in ion on cation Complex lactate, known

chloride oxalate of utmost strongly their citrate,

mononegative The

anions.

complex/chelate since the are

importance adsorbed elution.

exchange resin ions that are

separations special, formed obutyrate, strong of

measures with

required substances,

rapid

organic

tartrate, are

a-hydrox+s

EDTA,

TTA,

acetate, For as

thiocyanate

to form

moderately

complexes, Cf is listed

instance, 10 - 19.09+C.2

the dissociation by Fuger. 8

constant

of the EDTA

complex

IV. C.,

Extraction The only

Behavior rapid extraction of Bk -1-4 separation away from for Bk ‘3, the transcurium Cm+3, from HN03 and elements Cf+3 into . The that in-

volves

the

extraction

di(2 -ethylhexyl) ratio for of extraction the +3 state.

orthophosphoric coefficients 9 Procedure

acid-heptane for the +4 state

solutions than 10

is more

6 times

6 (Section

VU of this

report)

is based

on this

extraction. Cf, lanthanides 2 -ethylhexyl solutions. cf. ‘ 1 10 Es, Fm, and Cm can be separated into from each other and from phosphoric aqueous the acid, HC1 of

with

appropriate

extractions diphenyl are

di(2 -ethylhexyl) acid macro from

phosphoric These

acidjor

phosphoric with

extractions

effective

concentrations

8

The phate agent are

extractions discussed

of the by Best

lanthanides et al. , 13 12

and actinides and a purification

into of

tri-n-butyl Bk with

phos this re -

is described Magnussen

by Hulet. et al. 14

have

reported O. lM

the extraction

coefficients

of several bu.tfer into

of the transcurium TTA-toluene

elements The

from data

— ammonium

chloroacetate

solutions.

fit the equation

K=

E (H+)3 (HT )3(fHT )3

J

where organic given

E

is the extraction layer, and = 1 – f

coefficient, is the TTA

HT activity The

is the

TTA

concentration in the organic in Table I,

in the phases corrected

HT

coefficient are 15 listed

by

fHT

0.24

(HT)0.48.

data

to benzene from the

solvent

by Poskanzer obtained

and Foreman in toluene

who subtracted K.

O. 2 pH unit

pH5 ~ value

and recalculated

Table

I. tion

Extraction from Ion Bk+3

coefficients

(K) of the transcurium chloroacetate into

elements TTA-toluene

for

extrac

-

O. lM ammonium — K ==1.5X1O

solutions.

pH -7

for

507’.

Extraction 3.0 3.1 3. 1 3. 1

(Benzene)

Cf ‘3
E +3 Fm+3

8X 10-8 6X 10-8 8x1O -8

The for are La is

lanthanidee =4. O and

extract pH50 for

under Lu is

nearly -3.0,

the

same

conditions, -actinide

i. e. ,

PH50

so lanthanide from ions ions

separations earth by

no”t readily the +4

feasible. Zr-Hf Zr,

Group

separations

of the alkaline can be performed adjusted

group,

family, Hf, Pa, phase, .

and the Np, Pu,

oxygenated etc. from the

pre-extracting discarding the

a solution pH to 4.5

to pH 2,

organic

then This

adjusting step has

and extracting in any of the

the lanthanides currently used

and actinides procedure.

not been

reported

7

IV. D. -.

Ion Exchange ‘ The great

Chemistry between the various transcurium elements With by their has the exrelative

[

similarity

intensified ception elution have are of

interest No,

in and work

on their elements

ion exchange have resin. been While

behavior. identified separation

the transcurium from cation

positions devised

exchange

procedures they

been

which

do not make use. data from

use

of ion exchange

operation,

not presently In order

in general to compare

various

sources,

the ion-exchangecolumn volumes.!! resin position 55% bed of of

column This

eluate

volumes abbreviated

have

been

reduced is

to units

of Ilfree

volume,

FCV, for as

characteristic column dyes,

of a particular the elution

loading

and can be derived materials of the such

any

by finding etc.

unabsorbed the volume

organic

The

FCV

is about

column

bore.

IV. D. 1

Separations

of the

actinides

and lanthanides.

The

chloride

and thio cOm are 225

cyanate
plexes eluted with

complexes
of the from

of the actinides
When cation

are

stronger

than the corresponding
and actinides or Zeo-Carb the

lanthanides. strong or base

mixtures such

of Lanthanides as Dowex-50 are eluted

resins

12M HC1 —

2M NH4CNS, — are

the actinides Figure 2070 ethyl are

before the

lanthanides elution HC1 gas from from

and group positions at 20”C. Zeo-Carb Dowex-50 The as

separations from Dowex-50 Similar resin.

obtained. AG with

1 indicates alcohol with

relative with eluant

saturated the same

6, 16
225

separations Figure

obtained the relative 17

2 shows eluate.

elution

positions

using

1. 8M NH4CNS —

complexes

of the actinides and

in very are

strong such

completing that are anionic

agents species

such are under

13M H(ZL, —

IOM LiCl, — anionic

2M NH4CNS — of the

formed. the same

Similar

species

lanthanides are

not as probable using these

conditions, and anion 3 shows resin

so group exchange the with

separations resin. 18

possible

complex-

ing agents

Figure Dowex1 anion

relative

elution 6..

positions

of the actinides separations

from have

13M HC1. —

Slmllar

or better

8

Rh

Fm Cf, Es

Bk

Am Cm

Yb

1.0

0 o I 2 FREE
Fig. 1. Relative elution positions Dowex-50 AC with 20% ethyl alcohol elements appear as a group between

3 COLUMN

4 VOLUMES

5

6

of transplutonium actinides, Y, saturated (S= 12. 5~ ) with HC1. O. 3 and 3 free column volumee.

Yb, The

and Rh from transplutonic

Lo

Es

Cf

Bk

Cm

Am

0.01
2 3 4 FREE
Fig. Z. Dowex-50

5 COLUMN

6

7

8

9

VOLUMES
actinides from

Relative e lution positions of the transplutoniurn with 1. 8~ ammonium thioc~nate at 87 ‘C.

10

I

1

I

I

I

I

I

I

I

I

I

I

—LANTHANIDES Cf Bk Es Fm

m m

J

1
4 FREE 6 COLUMN

1
0

I

0

2

10
VOLUMES

12

14

Fig. 3. Relative elution positione actinides from Dowex - 1 with 13~HCl

of the lanthanides and at room temperature.

transplutonium””

11

I

I

I

I

I

I

I

I

I

I

I

I

I

Cm

Am

Es

Bk Cf

o

2

4 FREE

6 COLUMN

8

10
VOLUMES

12

14

Fig. Dowex-

4. Relative elution positions of the transplutonium 1 with 2. OM ammonium thiocyanate at 87 “C.

actinides

from

12

been shows

reported the

using

the elution

same

eluant

and Amberlite from 10M the same

IRA-400. resin

19

Figure

4

relative

positions of about

using and

2M NH4CNS. — elutions

Lithium equivalent

chloride to

solutions

give

adsorptions

13M HC1. — actinides with are O. 1~ eluted to 6~ from HC1, but cation very resins little like

When Dowex-50 between other Phillips impurities as shown

the transcurium J%G(4~o cross-linked)

separation from most by

the actinidea

and lanthanides

is obtained, 7 (Section

separations

cations

can be effected. 20 uses

Procedure

VII of this primarily 87°C are

report)

and Gatti of Ca,

a IIcleanupl!

column

operated at

to remove assembled is conducted

Fe, 5.

and Al.

Columns

operated is boiled

in Fig.

Trichloroethylene

and its vapor

A
\
ELUANT+

Fig. tions boiled
RESIN BED

5.

Column

apparatus

for

eluis con-

at 87°C.

Trichloroethylene the vapors column

in the flask, through the resin the

ducted around

jacket con-

bed,

and the

1
TRICHLOROETHYLENE -F

densed

vapor

returned

to the flask.

around viding tical

the column heat exchange

into

a condenser

and back column bubbles

to the boiling temperatures in the 100”C

flask, are

thus less and

proprac-

at 87 “C.

Higher of vapor

because with

of the formation adequate care,

solutions

resin

bed;

however,

temperatures

to

can be used.

13

IV. D. 2. separations relatively from its The elements Lating glycolic, cessfully tors the if

Separations

of the transcurium elements and NH4CNS,

elements from each

from other is

each are

other. obtained

While with

of the transcurium concentrated neighbor. most from convenient each acid other anions lactic, 21 . HC1

no element

separated

cleanly

and frequently has been to elute acid

used

method from

for

separation resin

of these with che -

them

cation

organic

Several and

anions

including acid obtained features

those have

of citric, been used sucfac are

tartaric, as eluants.

a-hydroxyis some is used,

obutyric is

While

advantage

in separation of the elution

a-~roxyisobutyrate with from

the general

same

any of the eluants. Dowex-50 elutions 16

Figure

6 is a typical
with at room

elution

curve

of the same

actinides butyrate. resin

( 12’70 cross-linked) are reported

ammonium temperature 225. 22

a-hydroxyiso from the

Similar

(4~0 cross Table

-linked)

and at 77°C elution

from

Zeo-Carb

II indicates resin with

the

positions

of the actinides acid, from The data

and lanthanides are et al. normalized , 21 Smith

from to

cation

a-hydroxyisobutyric been summarized 22

Cm=

1.00. 16

Data and

have

Choppin

and Hoffman, Since petition varied tr ation. anions ing the

Milsted

and Beadle.

the elution

position

of a particular phase’ that

element chelate,, determine acids

depends

on the comcan be concen chelating of varyeffect by and -

between at will These

the resin

and a solution the parameters

the position the chelate which form

by adjusting are the pH

of the

solution

of weak Figure

, and the total pH of solutions

acid

concentration.

7 shows sobutyric

the effect acid.

of ammonium obutyric

a-hydroxyi acid

The

of a change assuming

of a-hydroxyis Kd will

concentration

can be calculated is the same

be unchanged

when is

the anion 1. 1 X 10-4. members Cf equal and

concentration

the ionization The is much centration rare -earth

constant

of the acid

spacing than

between

the heavier between nearly

of the Bk for

series, constant been

Md pH

and

Fm,

less

the spacing Although

and confor 23

of eluant. separations

spacing

has

attained

in columns

utilizing

continuously

variable

eluants,

14

I.0

I

I

I

I

1

I

I

I

I

I

I

I

I

Cm

1

>
1: ;

v

a
u

> L

0.1

a J u c

0.01 o
2

~ 4 FREE 6 COLUMN 8 VOLUMES
curium actinides a-hydroxyiso

10

12

14

Fig. 6. Relative elution PO .sitione of curium and the trans from Dowex-50 127’0 cross -linked resin with pH 4.2 a~onium butyrate at 87 “C.

-

15

Table

II. resin

Elution with

positions

of actinides

and acid.

lanthanides

from

cation

exchange

a-hydrox~Bobutyric

Element

Dowex-50 25°C

4L70at

Zeo-Carb 77°C

225

at

Dowex-50 12~0 at 87 “C

Md Fm Es Cf Bk Cm Am Lu Yb Tm Er Ho Y Dy Tb Gd Eu Sm Pm Nd La Ce

--0.13 0.19 0.37 1.00 1.39 0.11 0.016 0.22

---0.21 -1.00 1.38 ----------

0.050 0.069 0.13 0,20 0.45 1.00 1.4 0.015 0.020 0.026 0.037 0.055 0.06 0.078” 0.14 0.28 0.39 0.71 1.2 2.1 r.

-0, 039 0.069 0.076 0.14 0.22 0.34 0.7 1.1 2.3

--.---.

-3.4

3,5

there

are .

no reports

that

this

has

been

accomplished

with

the transcurium

elements The of the graded lactic toward

flow

rate peake .

at which Figure

a column 8 shows

is

operated for

affects

the apparent

width

elution

the effect in water, at 87*G. flow rate

Dowex-50

127” resin, is O. 4~

to settle acid

at O. 5 to O. 25 cm/min is operated same

when The

the eluate

and the column half-widths

curve

is displaced resin resin is used.

greater

at the 5 or

when

coarser

A limiting est flow

half-width ratea.

of about

67’ is ‘found with the finest

and slow-

16

100

50

10

5

1.0 0.5 3.6 4.0 pH
Fig. 7. The peak position of Cff and Cm as a function of .pH’for O.-4~ ammonium a-hydroxyisobuty rate and Dowex-50, 12% cross -linked resin. The peak position of other lanthanides and actinides can be predicted from this curve and the table in the text.

4.4

4.8

17

I

I

I

...

I

o
FLOW

I
2
RATE

I
3

I
4

I

(ml/min/cm20F

COLUMN

AREA)

Fig. 8. Full width at half maximum (half-width) of the elution peak of curium from Dowex-50 12L70cross -linked resin with O. 4~ ammonium lactate at 87 “C on one particular column. Similar curves would be obtained with other eluants and other columns, but the resin particle size, temperature of operation, length-to-diameter ratio of the resin bed, technique, and the presence or absence of carriers or mass impurities all affect the absolute value of half-width at any flow rate. v. DISSOLUTION UDLING The emission. siderable These OF TI-IX transcurium Spontaneous numbers make SAMP-LES TRANSCURIUM elements fission are is also may AND SPECIAL ELEMENTS all unstable with respect mode to a particle con. PROBLEMS RELATED TO

a disintegration by some or larger

so that

of neutrons the handling very

be emitted

samples quantities

and targets of some Most chem-

facts

of microgram

transcurium ical operations

elements must

difficult

and potentially boxes,

hazardous. and in many

be carried

on in gloved

instances

18

remote free emits

-control

handling product 8

equipment contamination.

is

required For

even

after

the samples

are 252

of fission 42 X 10

instance, about

1 microgram

of Cf

neutrons/min of should survey

and presents 1 meter. have meters. are

a tolerance eq,uipped

working to handle

dose the as

of neutrons transcurium well

at a distance elements ~-y

Laboratories a-particle

and neutron

survey

meters

as the usual The

transcurium The

elements

produced isotopes

in at least are

three

different by heavy-ion

kinds

of target.

neutron-deficient or plutonium + 6 are ~12

produced such 246 as

bombardments

of uranium 238 92U

by reactions L + ~8Cf

—>40n

in which

the product target

atoms

collected The

on !Irecoil

catchersil

separate are

from

the bombarded by Thompson chemistry strong acid

material.

techniques

and difficulties 24 Briefly,

discussed the

and Muga3 lS done, solution

and Ghiorso

and Sikkeland. foil

when

the target

or catcher

is dissolved are

in the appropriate performed. handling When equipfor target

and the appropriate are produced

Reparations in this way

the tranacurium ment, target itself Since they decay the Pb such

elements boxes,

no special it may bombarded. technique stopped

as glove

may

be needed elements when

although are

be needed The is

preparation is seldom the recoil

if traneplutonium dissolved atoms or handled positive collected studied similar

the recoil when

used. gas, their of

retain

charges

in helium

can be electrostatically characteristics and Bi isotopes by can be have

as thin samples
without a-decay chemistry; half-lives alone Walton, are classic

and sometimes however, some

and particle may

energies

so that identification The experiments

a particle

measurements Sikkeland,

be unreliable. leading that every Lf

done

by Ghiorso, 102

and Seaborg in the sense

to the discovery advantage chemistry plates ments are are has

of element been taken on such washed without

(nobelium)

of these

nonchemical

separation collected HC1

techniques.

is done simply removed

electrostatically with concentrated

material,

the collector ele -

and the transcurium

dissolution

of the plate.

19

The nuclear

second

source Es

of tr”anscurium and Fm were

elements first

is the debris

from

thermo

-

explosions. produced produced

discovered

in filtered e~losion 238 . The

samples in which filter was destroy-

of the cloud they

by a multi-megaton by multiple digesting neutron

thermonuclear capture in U

had been

dis solved ing the HC104. its volume

by repeatedly traces fuming

it in concentrated by funing was then the

HN03 residue with

and finally

last The

of organic perchloric

material acid

in concentrated than 10 times 2

diluted

more

of

6N HC1, — was

and a separation on aliquots are that Ca,

procedure of this Fe, Na,

similar

to Procedure The major kind

(Section impurities usually

VII)

performed a solution radiation

solution. and Al.

massive

in such has so little last is

This

of sample

special

handling

equipment

is unnecessary.

The elements posed

and most

generally

encountered americium, doses

source or

of the transcurium that has been exrates sample alloy

uranium,

plutonium, neutron are

curium

to large

integrated techniques

in a reactor. by Thompson Ilslugll

The

production 3 The

and chemical is usually

discussed

and Muga.

produced material.

in an aluminum-clad Dissolution

of an otide by removing

or metal

of target in due

is accomplished filtering elements with HF or away strong

the aluminum resi-

6MNaO&M containing

— NaNO 3 solution, the transcurium. this

centrifuging from mineral

the insoluble

the aluminate acid (usually

solution, HC1, are or per-

and finally occasionally formed

“dissolving HC1 with

residue of

a trace

and

HN03).

These since

operations

by remote

control isotopes The

in shielded undergo complete

equipment while

the target

materials elements of a fractions VII is ,

and intermediate are rare are being -earth usually formed. fraction

fission

the transcurium including

separations, of the

the isolation and actinide 1 in Section

and the separation in the !Icave!l

Ianthanide Procedure

included

operation.

typical.

VI.

COUNTING C Ounting

PRC)CEDURES s amples or llthinll

AND

SOURCE

PREPARATIONS are usually prepared of course, and

of the transcurium because there are

elements no stable

IImaaa-freel!

carriers,

20

vACUUM

Fig. are

9.

Schematic

diagram

of vacuum filament,

volatilizer. the system

Carrier-free is evacuated, diet

Bolutiona and the a

evaporated

on the tungsten elements are

transcurium ,short-duration

volatilized pulse

onto the through

counting

by passing

high-current

‘the tungsten

filament.

because have drop

some

of the most The

useful sample

measurements is usually eluate

involve

the

a particles by evaporating or other

which a

short or

ranges.

prepared

either

several

drops

of column the counting

on a plate

of platinum

metal

and then carrier 5 mm between platinum salts than ond . tively

performing -free solution

operations,

or by evaporating filament This

the pure

onto

a tantalum long, and jar

or tungsten O. 1 mm a few thick.

approximately filament from is placed a 7/8-inch element more

wide,

30 to 50 mm

electrodes counting

in a vacuum disc,

millimeters 9,

away

as indicated are volatilized

in Fig. onto the

and the transcurium disc

(u~ually 10 amp This

oxides) of current

counting for

by allowing tenths

to flow

through

the filament temperature

a few

of a sec-

current all

raises

the filament

above

1400 “C and effeccounting

vaporizes

the transcurium

material.

Very

thin uniform

21

plates

can be prepared ,.

in this

way; rate

however, unless

the active they are

material

will

recoil

off the plates in air. No capture, elements particle

at an appreciable

heated

to about

500 “C

special or

counting

equipment Moat tracer

is used work

for

detection with

of

~,

electron-

a particles.

ie done of these

the transcurium have unique aby of iso to

by utilizing energies known .

the fact A particular

that

isotopes

elements

procese

or bombardment in terms =f252 or to of counts Cf254 a pulse An

can be traced per unit time, all Cf

introducing a specific

amounts,

measured (e. g. ,

longer-lived

isotope

to trace -height

topes)

and submitting
the is ratio of

the recovered
a counts and nearly

samples

analysis.

determine analyzer for work The ples of the

of several

isotopes. piece

a pulse-height equipment

a valuable

indispensable , rates

of counting

with high

the transcurium spontaneous

elements -fission

decay

are

utilized

in counting are

sam-

transcurium by taking

elements. advan~age

Spontaneous of the fact that

fission the

counters

easily proby

constructed duced

specific than

ionization

by fission

fragments electrical

in a counting pulses are

gas

is higher from

that produced fragments collector

a particles. by modifying voltages. tween 1/5

Large standard Satisfactory and 1/2

obtained

fission lower the

a-particle operation

counters is usually an

to operate obtained a plateau ~ -particle usually

with with

collector

be -

the voltage used collector and gas for

at which both a-

if found.
counting

The gas flow
are especially Semide-

proportional useful because

counters their

and can

voltages scintillation

be varied can also be

with used

ease. for

conductor

detectors

counters

tecting fiesima fragme,nta

and a particks.

22

VII.

SPECIFIC

SEPARATION

PROCEDURES

Procedure

1

This fraction

procedure

is for

separation plutonium on a 50-g are

of an impure

transcurium s lug. 25

element The process 1.0 g

from

a pile -irradiated

or americium slug

is designed of target

to be performed material, slug Am

aluminum also purified.

containing

O. 1 to

and Cm

The to 80°C NaOH

is placed

in a dissolver immersion is added.

pot heater.

surrounded Then 800

by an oil bath ml of solution

heated 6M in

with and

an electric

2M in NaN03 —

The aluminum reaction

violently

reacts

and goes material stain-

into solution is allowed less

(no heat required

after

starts ).

The insoluble

to settle and the supernate stick. The precipitate with NH3 gas,

is withdrawn is washed

through a sintered twice with 50-ml

steel filter

portions

of 2N NaOH — The -’shed

saturated precipitate After

and then washed

with 100 ml of H20.

is dissolved the residue

by adding 50 ml of 12M HC1 – O. lM ~03 — — 50 ml of llM LiCl — ie.added

and digesting.

is dissolved,

and the solution is evaporated

to 50 ml, to a 4-cm-diam
is heated ) The to 80 “C

The solution is transferred cross -linked
(Free walls column are

X 20-cm-long
with a water

Dowex-1
jacket.

10~0

resin

column

which ml.

volume with column

is -150 two

evaporator of 10M

container LiCl which

and column are allowed 300 to ml

washed the

50-ml rate

portions of about

run through of 10M LiCl —

at the through ions .

2 ml/min. to elute the

An additional lanthanides, are

is passed metal

the column The

alkaline next eluted

earths, with 200

and alkali ml of 6~

transplutonium remains

actinides

6N HC1. — HC1

Plutonium to 600 20 cm

on the column. through a Dowex-50 washed impurities eluted desired 12~0 with and with ele300

The resin ml of bed

is diluted and

ml and passed long. Ni, The

4 cm

in diam which

column

is then other are PH.

2M NH4C1 — the resin

removes

Cr,

and several actinides

converts

to the NH4 + form. obutyric in four acid adjusted

The

then The

O. 4M a-hydroxyis — ments are collected

to a suitable selected

or five

Ilcutstl

on the basis

of the ele -

Procedure

1 (Continued)

ments Fig. tion

desired

for

further

work is

and the number = 150 ml. enough The

of FCVie transcurium

predicted element

from frac -control

7 and the pH. thus obtained

Th’e F(ZV may be pure

to be processed by a procedure

without similar

remote

equipment cedures

and is usually 2 and 3 following.

further

purified

to Pro-

Procedure This from These day-old procedure fisaion are which through was devised

2 the transplutonium 10 15 to 1016 elements fissions. 26

to separate containing

product carried are

samples with

elements

yttrium

or lanthanum in HC1;

fluoride the

and hydroxide solution and An the lan -

precipitates, is passed most ethanol thanides.

subsequently anion resin

dissolved colurrms

resultant No, Pu,

several

to remove Zr used

U,

of the -HCl

remaining elution

fission from

products resin

(in particular, column is

and Te).

a cation

to remove

To prepare glass wool or

the ion exchange A slurry discarded.

columns,

the column

tips

are

plugged to settle, ml from

with

sand.

of reEin The resin

is introduced is washed deposited

and allowed by passing bed of resin,

and the eluant air

s upe mate through

several free

of

the column. is

A uniformly essential sample

bubbles 1. To

or channels, an aliquot Zr,

to a successful in a 40-ml

elution. tube, 10 mg/ml the twice add 2 drops

of the Te,

centrifuge of

each Using

of

10 mg/ml

and Sr carriers add NH40H and wash

and 1 drop

Y carrier. Cen-

phenolphthalein discard

indicator,

to precipitate

Y(OH)3. with

trifuge,
ml

the supernate,

the precipitate

O. 5- 1.0

H20. 2. Dissolve the precipitate test tube. a large in a minimum Add 2 drops of Fe cone or amount HF U, of per 3M ml HC1 and trans -

fer

to a polyethylene solution

of solution, HF to de-

(If the

contains

amount

add enough

24

Procedure

2 (Continued)

colorize for with

the

solution,

then

2 drops discard

per the

ml

in addition.

)

Let

the

solution

stand

5 minutes, O. 5 ml 3, of

centrifuge,

supernate,

and wash

the precipitate

2M HF — 2M HN03 — — the fluoride adding 2 ml

solution. by adding Transfer Sr 1 drop the saturated H3B03,

Dissolve and then

precipitate cone HC1, of

stirring, glass

solution

to a 40-ml boil disH20.

centrifuge

tube.

Add

2 drops the

10 mg/ml Y(OH)3 with twice

carrier

and then centrifuge, ml

the solution card

briefly.

Precipitate and wash

NH40H, with

the supernate, 4. Dissolve

the precipitate in 3 X

O. 5- 1.0

the precipitate

ml 10M HC1. —
Dowex - 1 AG

Add
anion of

1 drop cone HN03.
resin column solution 1 drop two with addi10M in the

Transfer
which has

the solution to a 5-cm
been O. lM 10 .mg/ml washed HN03, Zr with Push and anion Te

2-cm

several through

column with

volumes pressure.

10M HC1 — adding through treated

containing each tional HC1 initial of

After

carriers, which

pass have

the solution also been

10-cm containing

X 8-cm

columns

O. lM I+U’J03 (the —

small

column

contains

Pu

if present

solution). 5. Add NH40H to the combined discard the 10M HC1 — solution to precipitate the precipitate twice

Y(OH)3 with

.

Centrifuge, ml H20. Dissolve

supernate,

and wash

0.,5

6.
pass which Wash HC1

the precipitate through a l-cm washed

in a minimum X 2-cm with Dowex-50 several then

amount AG

of O. 1~ cation volumes

HC1

and

the solution has been

resin

column HC1.

previously with 1 ml

column 2 ml

of O. 1~

the column solution, 7. Using the

of O. lM HC1, — O. 5M HC1. —

of the

O. 006M HF – 0, lM — —

and finally a transfer l-cm has

1 ml pipet

and a minimum

of H20, X 2-cm

transfer Dowex-50

the cation resin of

resin column

from

column

to the top of a 12-cm washed the resin with has

which

been

previously After

several settled, with

column withdraw

volumes

the ethanol H20

-HCl

elutriant.

the excess of ethanol-

and. wash

out the column

above

the resin

a small

portion

25

Procedure

2 (Continued) ethanol every -HCl solution, uBing Collect tube. sufficient the de(See Fig. 1

HC1.

Elute the activity
to give

with

the 2070 1 drop 6-25) )

preseure sired for

approximately drops

45 seconds. centrifuge

fraction

(usually

in a 40-ml

typical This

elution solution

positions. will

be free for

of most co rn@ete

contaminants; separation each other

however, of the with

the column activities. 3.

separation The pure

can be repeatet activities can be

lanthanide Procedure

separated

from

Note: Some 7.

Several

variations

of steps “slurry solution

6 and 7 are onto from the step

reported bed

by different of the column into then the long

workers. in step column

prefer

loading prefer

the resin

resin

Others

to run the

6 directly

and to follow HC1. The

it with

10 to 20 column moves

volumes

of 2M HC1, — elements

the alcoholic about

2M wash — length

the transcurium are less perturbed

down

the column

10~e of the stirring

and they than

by the shrinkage

and accidental

of the

resin

otherwise.

Procedure This tions similar isobutyric tions. 27 1, Preparation A. (obtained is further and from of resin eluant free procedure ia for separating mass

3 the actinides from eacli other in solu It is a hydroxy separa-

of lanthanides,

other

impurities, et al. and

and radioactivities. except that it uses

to the procedure acid instead

of Thompson of lactic acid,

6.

consequently

gives

better

and, equipment. resin, Ave. 200-400 mesh spheres Calif. ), O. 5

Dowex-50 Bio-Rad for from The

12~0 cross-linked Labs. , 32nd

and Griffin the fraction

, Richmond, settles

graded

size

by selecting . resin

that

between

O. 25 cm/min B.

water

graded stored

is washed

alternately form.

with

12M HC1 and —

NH40H

and finally

in the ammonium

26

Procedure

3 (Continued)

\

c. acid diluted

The

eluant

is prepared the pH

from

commercial 3.8 7. )

a-hydroxyisobutyric and 4.4 Phenol to give may the

to O. 4M with — time -peak is

adjusted

between Fig.

denired until

elution

separation.

(See the

be added

the solution D.

O. OIM to prevent — is long set over

growth 5.

of mold. The column The bore is 2 mm

Apparatus 10 cm

up as in Fig. the capillary

in diam with ene

and about wool.

region.

tip is plugged -

glass

. The

column with

is heated distilled

to the boiling water; then

point small into

of trichloroethyl amounts of resin until a

and the bore are bed added 5 cm ml

is filled

slurry settled

to the column in height

and allowed The

to settle excess remove is

the bore water

is obtained. is added

distilled trace lowered, or two

is removed Just

and several prior column

of eluant the column, with

to further

impurities.

to using

the eluant water,

reservoir

the top of the of distilled water

is washed

distilled the HN03 dryness column.

and a drop

is allowed 2. is

to run into An HC1 or

solution

containing

the actinide cone,

element and diluted

mixture with bed resin to run and

evaporated of hot

to near 0.05

in a 5-ml This solution

centrifuge

=s0. 1 ml allowed bed into are

MHC1. The 50 pl

is transferred of the column which

to the above

resin the

to run through, washed with The

cone

and sides

of

O. 05M HC1 — procedure is washed

solution

is allowed

the resin. 3. The

washing cone

is repeated. with 50 pl of eluant column. elution. with hot eluant is which The is then drop

centrifuge

transferred to fall from 4. carefully lifted are

to the column the column bore

and allowed this is

to run into “drop the

the

first

after

1 1! of the resin bed, Fig.

The

of the column stirring flow of

above

is filled and the 8).

so as to avoid

the resin rate to (see

eluant

reservoir

to provide obtained 5. with

the desired flow rates

Satisfactory minute. which is dried

separations

1/2

1 drop

per

Each

drop

is collected to red heat

on a platinum in an induction

plate

under the last

a

heat

lamp

and heated

heater

to remove

Procedure”9
tiacem of organic The material. Phton

(Comtinu@
are ready to co~tn

.,

q pprokte
.

Fig.

7 and fro”m Table mriatim

elution pomitionp can b. predicted from the curve in . ~, assuming a 3-&op free column volume; however,
..

q light

in aluent and rada

make it desirable actide

to Ilcalibrtitefi bd”ore

eech are
cepi of

column with a trecer attempted. be followed,
col~

of

q oma

trensplutamium

q eparationfi

If cirrterm
but tie. for eech col~

me

includ6d In the qolution tie
sise hould be ~ueted of carrier,

sarne procedure

to provide

0.4

Cmz

q rea

milhquinlent the

eqd tie length of the column

should be at leant

10 timeh

diameter.

Rocedure

4

.,

This
re~in dde

procedure

•e~ratem

the actinidm

from the laa~des. the acdnide element-,

6

Dowexlantlm-

1

is ueed “with en HC1 ictlvitiem,

fiolutioa conMaing 1 mg lan-um

end qbout

carrier. 200-400 from me-h ~pherem,

A. graded water. by

Dowex-1

“8% cromm-linked”remin, fraction tit settles

im dne ia NH40H

q electkg

O. 15 to 0.25 cm@n with 12# HCl -d

The graded remin is wmhed k the chloride form

dternatbly mfter c ftil

and i- stored B. with HCl disaipkte 13g . C. illary

HCL -ah. 8n81ytkl grade HCl

Elu8nt is prepred IB88. Immermiag the heat.

by •atkua~ the bottle-

commercial

in roo=tempermture

tAp weter helps

The find

caacentrmtion

of acid -t 20-22 “C will be about

The cohmm is prepared
q

by

q ttaching

q

qectiom of 3-mm-diem
* . tip with glmm wool, . The columa uee.

cap-

tubing to

15-ml . .

teat.Afage

cone,

p8cMng

8nd filling

the bcke

to m height with

of 5 cm with the redn.
and water

-bould

be alterxmtely

washed

elumit

before

The final w?-h i-

m8de with eluant. 1. The solution ceat~uge to be purified cone.
The ievaporated is placed to -30 pl with an

qir je”t in

q

5-ml

cone

in an ice -&ater

bath

aa

Procedure

4 (Continued)

and the solution 2. first drop to fall which

saturated The solution this

with is is

HC1

from

a gas

cylinder. column. The with repeated. 30 pl

transferred “drop

to the top of the 1. “ The This cone wash

after

called

is rinsed is then

of eluant

ia transferred

to the column.

One milliliter
are collected per

of eluant is carefully
through drop 3. with drop 12. The

placed
flow

on top of the column and drops
can be maintained and rubber stopper. above and the 1 ml resin are the of and found 10M — at about 3

rate

minutes

a hypodermic drop 12 has cone

syringe fallen,

After

the eluant under

is removed

resin, HCL elutes

a 15-ml is placed

centrifuge

is placed This Am,

the column, through

on top of the

resin.

is passed Cm,

the transcurium 1- 12.. U and

elements. Pu

and the lanthanides state) remain

in drops resin

(in the IV or VI oxidation removed.

on the

and may

be subsequently

Procedure This particle procedure 27 . Is for 253 purification .

5 of Md recoils produced foil by a

bombardment Other target area to pass

of Es actinide

It is typical

of the catche,r are 253 similarly

chemical handled. ,

techniques. The X l/4-in. allowed onto

targets of = 109 O. 002-in,

and products atoms -thick of Es gold and

consisted of larger through -thick

electroplated A 48-Mev offll the

on a l/32-in. a beam Md was

foil.

the gold foil

gold

target

foil foil.

Ilknock

atoms

a O. 0001 -in. 1. The

Ilcatcherri dissolved

catcher” liquid

was

in aqua for

regi?, =S1 min. a 2-mm Fig.

and the gold extracted

with

an equal 2. The

volume phase resin minute. was

of ethyl was heated The

acetate

aqueous - 1 anion per

passed

through (see

-diam

X l-cm-long of about

bed five

of Dowex 30-pl

to 87 “C original

9A at a rate 5 drops a. jet

drops

volume

plus with

containing

the actinide

elements

collected

and evaporated

of hot air.

Procedure

5 (Continued)

3. 2-mm heated solution with flow were

Tracer

Es

253

was bed

added

and the

solution

was

passed

through cation with

a resin

-diam

by 5-cm-long The

of Dowex-50 actinides acid

X 12 ammonia-form were selectively eluted to the The

to 87 ‘C. of

adsorbed

a 0.4M —

a-hydroxyisobutyric hydroxide. The

which was drops

had been passed per 15-19,

adjusted through

pH s=4. O colurr&at a

ammonium rate

eluant

of approximately in drops

four 20-pl
8-13, Fm

minute. Es

Md

fractione and

collected

in drops

in drops

27-31,

Cf in drops

39-47.

Procedure This containing 1. 16M HN03 — added volume 2. times each with time. 3. step procedure lanthanides The . solution After the the is for oxidation

6 of are two Bk from a solution

and extraction

ahd actinides. is evaporated last evaporation,

9

No

carriers dryneaa Bample 1~

used. or three and times KBr03 1). The with is

to near the

is diluted

to make of the V ml

Eolution is

10M in HN03 — measured HDEP

and

in KBr03 (called solution – lM V

(Note

solution

in milliliter~ 2.)-heptane 10M HN03

in the following). three 3 minutes

of O. 15~

mote

is washed for

V ml The The

of freHhly aqueous

prepared are

KBr03,

phases step

dincarded, with the organic phase from

solution

from

1 is contacted are

~ four 3 minutes 4. The organic

and the phases phase from

Beparated. twice The for wash 3 minutes solutions with are

step –

3 is washed lM KBr03.

V ml

of freshly

prepared

10M

HN03

di.qcarded. 5. utes into The V ml phaae washed organic phase from 10M step HN03 4 is back-extracted — 1. 5M H202 — for 3 min The

of freshly ia discarded. aqueous

prepared

solution.

organic

6.

The

phaee

from

Step

5 is washed,

first

with

V ml of

O. 15M

90

Procedure

6 (Continued)

HDEP The Bk, ides

– heptane

for

3 minutes, are

and then

with

V ml

of heptane containB

for

3 minute of the

B.

organic

phaEeB

dimcarded; of of

the aqueouB * 104 -10 from from all

phaEe other and

_97~0

decontaminated except Ge,

by factors and by factors

lanthanides Cf. (Note

and actin3.)

6

Cm

Note B 1. with little 2. PH(OH), O. lM _ KBr03 may be substituted at all points calling for 1~ KBr03

or no decrease HDEP

in yield. orthophoephoric form from the acid, Victor Stewart

is di(kthylhexyl) in impure

and iB available

[1
c8H170 Chemical and H. W. similar Cf and Cm.

2 Works. Crandall,

It is purified J. Am. 3. this for Chem.

by the procedures Sot. 73, — 1377

reported (1951). 11

by D. C.

Cunningham extracting were

and Wallmann

have

used

a procedure

to Solution

submicrogram

quantitie8

of Bk from

volumes

reduced

to Bubmicroliter

quantities.

Procedure This curium 1. AG H+ procedure 17 is for removal

7 impurities from tracer trans-

of macro

samples.

A jacketed

column resin last),

for

operation rate

at 87°C

is prepared.

Dowex-50 is used 3, in the steps

47’O cross-linked form (HC1 lB. wash

(settling

O. 5 to O. 25 cm/min) otherwise

and prepared bore is 3 mm

as in Procedure

1A and num

The

column

in diam

and the tip coneiBts out with a No.

of a platiThie

rod fused

to the glass 13-I.U

capillary drope.

and bored

64 drill.

tip delivers 2. and then with

uniform The solution

to be purified

is prepared

so as The

to be O. lM wallB

in HC1 rinBed

allowed

to pas B through portions

the column.

column

are

several 3.

1OO-P1 1 ml

of O. lM HC1. — is carefully introduced above the resin bed

About

of 2M HC1 —

31

Procedure

7 (Continued)

and forced 50 drops 4. and forced drope drop Other are

through have The been

the

resin

at the rate

of about

6 drops

per

minute

until

collected. 2M HC1 is withdrawn rate and 1 ml per elute the of 6M HC1 minute close’ until together from is added 30 or 40 arnund 3).

remaining

through collected.

the resin The from as

at the

of 6 drops elemente

transcurium

80 (counting cations elute

the beginning, indicated

including III.

50 drope

step

in Table

32

Procedure

7 (Contiriued)

Table

III.

Order

of elution of cations

from

resin

column

in Procedure

7.

Free Cationsa Au Pd Pt Bi Cd Pb Li Mo Cu Fe Na Be Mg Drop No,

Column Volumes (after first)

1
1

=’=7

13 16 17

22

2.6

of 2MHC1

24

26 28
30

Rb Ni

1
1
and

37

Ca
Al Sr Ba Actinidea Lanthanidea

53

2.8

64

3.6
4.0

70

75-85
96

4,4

-5.1

Zr
a

5.9

The

oxidation

rotate of these

ionE wan not

specified. most will (full

Where etable handle widths These

que ationa and 0.1 soluble to maxhave ions in

exist,

it can be aesumed

that the oxidation The colunm

state specified

2N HC1 is the one indicated. — 0.2 mg of macro impurities, ima) generally run

and peak the

half-width

at half data

6-8% under
to free and Pb) depend The

conditions volume appreciably

specified. units because

not all been (Au, Pd, Pt,

reduced Bi, Cd, will

column move

several

of the

in O.1~

HC1 and their from which the are

elution material not

position

on the volume positions

of the

solution

is adsorbed. affected.

of the actinidee

and lanthanide’s

similarly

33

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Their Their 2. 3. B. S. B. G.

and a Presentation ‘f UC RL-86 J. M, Chem. Louis

of the Different 1959). 36, — (January,

Methods

15 (April, Educ. Muga,

1959). and Peace-

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Elements. 2nd, Geneva,

U. N.

15/P/825. , II Addison-Wesley Pub-

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, Reading, T.

1958. of the Actinide Elements, “

Katz

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Inorg,

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L.

B,

Magnussen

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National

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16,

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(1956).

Smith

and D.

C.

Hoffman,

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Chem.

~,

243-7

17.

J.

P.

Surls

and G.

R.

Choppin,.

J.

Inorg.

& Nuclear

Chem.

~,

62-73

(1957), 18.

E.

K.

Hulet,

R.

G. from

Gutmacher, the

and H.

S.

Coops,

“Group

Separation

of the Actinides (1960). 19. J. Milsted,

Lanthanides

by Ion Exchange,

11 UCRL-5639

Atomic to S. and R.

Energy G,

Establishment, reported Calif.

Harwell,

England}

private

communication 20. L. Phillips

Thompson Univ.

in reference.

5 above.

Gatti,

, Berkeley,

unpublished

dab.

(1960). 21. G, R. Choppin, Chem. B. ~, G. Harvey, and S. G. Thompson, J. Inorg.

Nuclear 22. 23. 24.

66 (1956).
B. Phys. T. Beadle, Chem. J, Inorg. & Nuclear Chem, ~, 248 (1956).

J. Milated
W. E,

and A. J, and

Nervik,

59, — 690 (1955).
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A. Ghiorso
menta, Geneva, ‘+ Proc. 1958, Higgins

Sikkeland, Lntern.

U. N.

Con-f,

Peaceful

Atomic

15/P/2440. and W, 2nd, J. W. W. T. Crane, 1958, H. Proc. U.N. Conf. Peaceful Uses

25.

G.

H.

Atomic 26.

Energy,

Geneva, Barnes,

17/P/1883. L. Smith, and W. R. Daniele., un-

D. C. Hoffman,
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procedure B. G.

used Harvey,

at Los G. 98, —

Alamos R.

Scientific S. G.

Laboratory Thompson,

(1958). and

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A. G.

Ghiorso, T. Seaborg,

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Phys.
Mmulm, W

Rev.

1518

(1955).

uSMC OHI-

OFTuhnlcal

lnfarwdlm

Rldw, T—

?E

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