NAS-NS-3013

Page 1

1,’ National

~cademy

~~

v

of

Sciences

National

Research Council

9

NUCLEAR

SCIENCE SERIES

The Radiochemistry

of

Bery

Ilium

COMMITTEE

ON NUCLEAR

L. F. CURTISS, Chairman National Bureau of Stadards

SCIENCE

ROBLEY D. EVANS, Wce Chairman M&3 BWhU8ettB huvtituteof Technology

J. A. DeJUREN, Secretury 1 We,vtinghouse Electric Corporation H. J. CURTIS Brook.haven National Laboratory

G. G. MANOV Tracerlah, Inc.

WUEL EPSTEIN California Inetitute of Technology

W. WAYNE MEINKE University of Michigau

HERBERT GOLDSTELN Nuclear Development Co~ration America

A. H. SNELL Oak Ridge National Laboratory

of

E. A. UEHLING University of Washington

H. J. GOMBERG University of Michigan

D. M. VAN PATTER Bartol Research Foundation

E. D. KLEMA Northwestern Universi@ ROBERT L. PLATZMAN Argonne National Laboratory

LIAISON

MEMBERS

PAUL C. AEBERSOLD Atomic Energy Commimion

W. D. URRY U. S. Air Force

J. HOWARD McMILLEN . National Science Foundation

WILLIAM E. WRIGHT Office of Naval Reseamh

SUBCOMMITTEE

ON

RADIOCHEMISTRY

W. WAYNE MEINKE, Chairman University of Michigsn

HAROLD KIRBY Mound Laboratory

GREGORY R. CHOPPIN Florida State University

GEORGE LEDDICOTTE Oak Ridge National Laboratory

GEORGE A. COWAN Los Ah3DiOt3 Eeientific Laboratory

JULLAN NTELSEN Hanford Laboratories

ARTHUR W. FAIRHALL Universi@ of Washington

ELLIS P, STEINBERG Argonne National Laboratory

JEROME HUDIS Brookhaven National Laboratory

PETER C. STEVENSON University of California (Livermore)

EARL HYDE University of Celifom.ia (Berkeley)

LEO YAFFE McGU1 University

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

WlLLL4M MARLOW National Bureau of Stmdards

C~STRY-RADIATION

The Radiochemistry

ANDR4DIOCHEMIST

of Beryllium

By A. W. FAIRHALL Department University Seattle,

of Chemistry of Washington

Washington

bfZly 1960

Subcommittee National

Academy

on Radiochemistry

of Sciences

窶年ational

Research

Council

Prtnted in USA. Price $0.75. Aveileble from the Office of Technical Services, Depmtmentof Commerce, Waehiagtm 2S,D. C.

FOREWORD The Subcommittee on Radiochemistry ie one of a number of Subcommittees working under the Committee on Nuclear Science within the National Academy of Sciences-liational Research Couucil. and university Its mmbers represent government, industrial, laboratories in the areas of nuclear chemistry end analytical chemistry. The Subcommittee has concerned itself with those areas of nuclear science which involve the chemist, such as the collection sad distribution of radiochemical procedures, the establishment of specifications for radiochemically pure reagents, the problems of stockpiling uncontaminated matsrials, the availability of cyclotron timm for service irradiations, the place of radiochemistry in the undergraduate college progrsm, etc. Thin series of monographs has grown out of the need for up-to-date compilation of radiochemical information and procedures . The Subcommittee has endeavored to present a series and which which will be of maximum use to the. working ecientiat contains the latast available information. Each monograph collects in one volume ‘the pertinent information required far work with an individual elemnt or a group of radiochemical closely related elements. An expert in the radiwhemistry of the particular element has written the monograph, following a stamdard formmt developed by the Subccaumittee. The Atomic Energy Commission haa sponsored the printing of the series. The Subcommittee is confident these publications will be useful not only to the radiochemiat but also to the research worker in other fie~ds such as physics, biochemistry or medicine who wishes to use radiochemical techniques to solve a spcific problem.

W. Wayne Meimke, Chairman Subcommittee on Radiochemistry

iii

CONTENTS I.

GENERAL

REVIEWS

CHEMISTRY II. III.

Iv.

ISOTOPES REVIEW

INORGMHC

AND

ANALYTIC&L 1

OF BERYLLIUM

2

OF BERYLLIUM OF BERYLLIUM

CHEMISTRY

OF INTEREST

TO

RADIOCHEMISTS

3

i.

General

3

2.

Complex

3.

Chelate

Complexes

of Beryllium

5

4.

Soluble

Compounds

of BerylliuIxI

8.

5.

Insoluble

6.

Solvent

7.

Ion Exchange

Ccmsiderationa

COUNT~G

4

Ions of Beryllium

Compounds Extraction

PROCEDURES COMPOUNDS

v.

OF THE

of Beryllium

Behavior

FOR

9

of Beryllium

10

Compounds

16”

of Beryllium

DISSOLVING

SAMPLES

CONTAINING 21

OF BERYLLIUM TECHNIQUES

FOR USE WITH

ISOTOPES

OF 22

BERYLLIUM

VI.

COLLECTION FOR

OF DETAILED

BERYLLIUM

RADIOCHEMICAL

PROCEDURES 28

The Radiochemistry

A. W. FAIRHALL Department of Chemistry of Washington, Seattle, May i960

University

I.

GENERIL REVIEWS OF BERYLLIUM

“Ber@ium”, Compounds”,

of Beryllium”

OF THE

INORGANIC

Washington

AND ANALYTICAL

CHEMISTRY

Pp ~97-2i8, VO1. I. of “The Chemical Elements and Their N. V. Sidgwick, Oxford University” Press, London, 1950.

“Beryllium” ,, PP 204-248, Inorganic and Theoretical and Co. , London, i923.

VO1. IV of “A Comprehensive Chemistry”, J. W. Mellor,

Gmelinis Handbuch der Anorganischen Chemie, Verlag Chemie G. m. b.H. , Berlin, i930.

System

Treatise Longmans,

Nr.

26, 8th Edition,

“Applied Inorganic Analysis”, W. F. Chapter 32, pp 5i6-523, G. E. F. Lundell, H. A. Bright and J. I. Hoffman, 2nd edition, Wiley aqd Sons, Inc. , New York (i953). “Beryllium” ~ PP 137-148j Analysis”, N. H. Furman, Inc. , New York, i9 39.

on Green

Hillebrand, John

VO1. I of “SCOti’S E$kmdard Methods of Chemical editor, fifth edition, D. Van Nostrand CO. ,

L. W. Neidrach, A. M. Mitchell and C. J. Rodden, pp 350-359, “Analytical Chemistry of the Manhattan Project”, C. J. Rodden, editor-inchief, McGraw -Hill Book Co. , Inc. , New York, i950. “Non-ferrous myst q

Metallurgical 619 (1956).

Analysis.

A Review.

*

“

G. W. C.

MUner,

This report was prepared at the request of the Subcommittee on Radiochemistry of the Committee on Nuclear Science of the National Research Council as a contribution to a proposed master file on the radiochemistry of the elements.

1

II.

ISOTOPES o~y

mass

OF BERYLLIUM

<our isotopes

numbers

of beryllium

are lmowTI to exist, those having 8 One of these, Be , is completely

7, 8, 9 and 10.

unstable, breaking up tito two alpha particles in a time less than ~o-i5 sec. A short-lived isotope of mass 6 has been reportedi but its existence

is doubtful.

one which is stable,

and constitutes

an abundant element, A1203 -6 beryllium

Of the remaining

although

is rather

Si02,

three,

the element.

its principal

wide spread

isotopes

both relatively 54 day4,

of masses long-lived

decaying

7 and iO are nuclides.

by K-electron

beryl,

is not 3 Be O.

in occurrence.

of rocks2 is only about 3 ppm, -i3 only about 5 x i O g/ml of the element.

The

Beryllium

mineral,

content

contains

Be9 is the only

The average 3 and sea water

of interest

b that they are

Be 7 has a haJf-life

capture

to stable

decays,

Li7.

of close Of these

42% go to a O. 477 Mev. excited state 5 go to the ground state. The only detectable

of Li7

the O. 477 Mev

much too soft to be

y ray,

the x-rays

of Li being

detectable excited

by present techniques. . st+te of Li’ is uncertdn

Because a nuclide

of its rather

of some

artificially

at lower

interest

reactions

energies

tiduced

in light

duction

of Be 7 by cosmic 13-15 been observed.

and convenient

It arises

ratio

therefore

is

of 12% to the

cent.

in the study of nuclear

in the laboratory.

in the nuclear

The branching

low mass

and the remsinder

radiation

by 5 - iO per

to

hslf-life,

-7

is

reactions

as a spallation

produced 6-40 product

at ,high energies,

elements

is of some

ray bombardment

and its production ii, 12 interest. Pro-

of the atmosphere

has also

io isotope of beryllium, Be , is quite long lived, with 84 a half-lMe of 2.5 x iO y. It decays by f!- emissi& to the ground io state of stable B , and @ keeping with the long half-life and The heaviest

consequent of Beio studied product

slow bufld -up to detectable

m “ nuclear

intensitiess,

the production

reactions

in the laboratory is not likely to be 10 is produced as a spallation radio -chemically. However, Be i6 i7 of cosmic ray action on the atmosphere ! and on meteorites,

so that its occurrence

in nature

is of considerable

geochemist.

2

interest

to the

i8

Ill

REVIEW OF BERYLLIUM JUIDIOCHEMISTS i.

General

element topic

which

which

separation

to facilitate

ical

of the radioactive

of beryllium

governed tolerate

large

counting

should be as weightless procedures

of beryllium

is being

of the

analyzed.

Iso -

are often

of beryllium

is of interest:

efficiency,

whereas

as possible.

the is

Be 7 csn

interfering

samples

Fortunately

are available horn

without

added

the them-

is to be added to the sample

of carrier

ranging

by the amount

k the case

amounts

for beryllium

amounts

species.

which

the chemical

and to determine

of the two radioisotopes

relatively

the subsequent

TO

element

of milligrams,

the separations

carrier

by which

which

of the order

to the sample

amount

in part

in the sample

in amounts

recovery

of a particular

are used are governed

is present

carrier,

OF INTEREST

Considerations

In any radiochemical procedures

CHEMISTRY

with

for counting

Be

io

radiochemical

which efficiently

sub-microgram

will

isolate

up to macro

amounts . III performing beryllium t~xic

present

ele ment.

through

chemics3

separations

Care

should be exercised

compounds.

Beryllium keeping

is the lightest

+ 2.

of a group

shows

of the next higher closely

chemical

group:

resembles

member

solutions

chart

of beryllium

are

spilled

than it does

II elements.

In

it has only one oxidation

of the rule

resemblance

in its chemical

aluminum

ingestion

of the group

good example

a strong

is a very

off at once.

in the periodic

It is a very

of

of dust or volatile

If beryllium-containing

with its position

number,

to avoid

or by inhalation

on the skin they should be rinsed

quantities

that bery ~um

it must be born in mtid

the mouth via pipettes

beryllium

with sensible

to the second

behavior other

that the first

beryllium

members

member member

more

of the group

H

elements. Because

of the electropositive

of only one oxidation tracer

species

is completely hydrolyse carrier

presents

colloidal

exchange

for the ion,

no problem

homogeneous.

and form -tracer

number

nature

of beryllium, exchange

between

so long as the sample

The strong

tendency

aggregates

above

be carried

and the existence

out in fairly 3

carrier containing

of beryllium

pH 5 requires acid

solution.

to that

and them

Many of the chemical

properties

in its radiochemical

separations

form

These

complex 2.

ions.

Complex

Because

size

tendency

toward

simple

uniformly

have

atom,

for understanding amphoteric beryllium

The aqueous to several

are

important

with its ability

be treated

to

first.

tendency

the formation

of complexes. of water

tendency

given

toward

of crystallization a basis

and the

constants

for several

I.

way by its power

proportions

ion

Thus the

hydrolysis

Stability

in Table

of any soluble

the beryllium

of the Be++ ion forms,

of Be++ Ion toward

peculiar

molecular

charge,

of this species. are

solution

and its double

4 molecules

the strong

complexes

up in a rather

will

and the hydration

properties

The strong

are associated

complexes

has a strong

per beryllium

which

Ions of Beryllium

of its small

salts

of beryllium

complex

to dissolve

salt of beryllium

of beryllium

oxide

formation

shows

beryllium

oxide.

can dissolve

up

or hydroxide,

The reason for this is apparently the tendency to form the complex ion i+ , where BeO molecules have replaced H20 molecules in Be(OBe)4 the aquo complex.

Table Chelating

I.

Stability

for

3,K

Beryllium

Chelates

log K2

log Ki

Agent

EDTA

log K3

Reference

q.

2

G

ace~lacet

oxalic

Constants

one

The complex

soluble behatior

9.2

7.8

7.8

6.7

2 ..

48 49

formed

between

as it is the only oxalate

k water.

2

2.54

acid

inasmuch

7.7

4.0

acid

phosphoric

8.2

i.’8

Be

++

and C204

of a divalent

It is a good illustration

of beryllium

from

4

= , is of some

metal

which

of the difference

that of the rematider

2

1.4

interest

is freely in chemical

of the group

II

elements.

The low degree

that it exists

as a chelate

The complex noting,

insoluble

between ion forms

closely

the sulfate

precipitate

in radiochemical

and finds

analyses.

can be used to advantage fluorides one,

to render

presumably This

forms

because tions

fluoroberyllate

fused

are

compounds

strong

of excess

solution

procedures

derived

anion.

from

acids.

which they play which

acid (abbreviated complex

of other

of -

A large

will

6

number h For

should be consulted. special

mention

be mentioned

EDTA),

constants

metal

a special

in radiochemical

3.8 for beryllium

common

or sse

for

separa

-

is

and for the reason

with many metals

stabili~

compounds,

agents 2i of beqllium.

which deserve

of these

II lists

-keto

as chelating

literature

agents

of

charged.

and hydroxyquinones,

the original

roles

The value

exchange

into two groups

hydro~

amounts

a much stronger

than those

either

of trace

ethylenediammtietetraacetic

ions with EDTA.

technique

with a variety

or negatively

have been studied

The first

Table

3.

the phosphate

cation

may be divided

of czrbo~lic

four chelating

with beryllium.

H ~130

at pH 8.5-9,

carbonate

which limits

complexes

comple~es

determination

of the important

that it forms

chelate

they are neutral are

with

of Beryllium

$ -keto -esters

of beryllium.

smaller

of beryllium

is a fairly

of a comph+x

an

2

derivatives

-keto

of these

There

These

complexes

the calorimetric details

are

by the addition

complex

numerous

to whether

of covalent

of hydro~

of sodium

are to be used in certain

Complexes

~ -keto -enols,

class

which

agents.

Neutral i.e.

of a BeH2P04

Chelate

completing

precipitation

nature

in i 0~0 (~4)2C0s

has been reported.

Beryllium

according

destroyed

of the formation

of solutions

3.

a use h the final

which

forms

has been used in an ion exchange 20 of beryllium from copper and nickel.

The formation

separations

BaBeF4

of beryllium

for the separation

content

Thus

mineral specimens 19 soluble. The complex

ion is soluble

proper@

anion.

ion is worth

anion BeF4=,

where

them

because

is evidence

and fluoride

the complex

The soluble

but may be completely Beryllium

beryllium

fluoride

very

of the compound

complex.

formed

Excess

resembles

of ionization

than it does

a number

of metal

is sufficiently

ions that sever+

useful

separations

may be carried

other

species.

metal

with ammonia if excess

is present.

to prevent

beryllium

hydroxide

of aluminum , without Other

interference

examples

from

may be precipitated

the latter

of similar

precipitating,

applications

will

later.

A second The chelate melting

example,

h the presence

EDTA

be cited

For

out using EDTA

very

useful

compound

(i080 ) volatile

in organic

solvents.

Table

chelating

beryllium

agent for beryllium acetylacetonate,

(b. p. 2700) solid, This

chelate

11, Formation

Constants

Be(C5H70Z)Z

insoluble

compound

is acetylacetone.

in water

forms

of Metal

but soluble

the basis

- EDTA

is a low

for a

Completes

A!@L

Cation

log K

25.9

Europium

i7. 35

25. i

Samarium

i7. 14

Iridium

24.95

Neodymium

i6. 6i

Thorium

23.2

Ztic

16.50

Scandium

23.1

Cadmium

16.46

Mercury

2i.80

Praseodymium

16.40

Gallium

20.27

Cobalt

16. 3i

Lutetium

i9.83

Aluminum

16.13

Ytterbium

i9. 51

Cerium

i5.98

Thulium

19.32

Lanthanum

15.50

Erbium

18.85

Iron

14.3

Copper

is. so

Msnganese

Vanadyl

i8. 77

Vanadium

Nickel

18.62

C&lcium

iO. 96

Dysprosium

i8. 30

Hydrogen

io. 22

Yttrium

18.09

Magnesium

8.69

Lead

i8. 04

Strontium

8.63

Terbium

17.93

Barium

7.76

Gadolinium

i7. 37,

Beryllium

3.8

Cation Vanadium Iron

(ILI)

(III)

M ‘n+Y

-4

(III)

(II)

for

Beryllium,

i4. 04 (II)

12.70

~(n-4) *

K=+n

MYn-4

M a In solutions

a

of ionic which

strength is from

O. i.

Data from

reference

6

2.

Y-4 reference

22, except

solvent

extraction

carrier-free chelate

procedure

tracer

compound,

tracer

to avoid

A third

loss

thenoyltrifluor

acetylacetone The fourth

chelating

acid.

complex

compounds

in reducing

acetylacetone 23 is useful

oacetone

as the

of the

solutions

of

has been used,

in

for the isolation

(TTA).

The

of beryllium

complex

a property

beryllium

acetate,

compounds

with

which

which

is formed

unique

in forming

acids,

of the general

makes

of beryllium

and volatility

of the complex

(b. p.

separations of

formula

soluble

in organic

is the acetate, beryllium

It is generally

in radiochemical

concerned.

a series

are non-ionized,

by treattig

anhydride.

are

to beryllium

The best known of these

acid or acetic

extraction

of beryllium

of significance

is almost

These

and volatile.

stabflity

agent

amounts

with carboxylic

solvents,

with acetic

tracer

Beryllium

(0- CO-R)6.

solvent

to the volatility

and to decompose,

where

is acetic

Be40

Owing

as small

a solvent-extraction separation of beryllium from a number 24 cations. The non-volatili~ of this complex is an advsntage

of other over

agent which

is slow to form

possible

where

of the tracer.

chelating

of beryllium

must be exercised

to dryness

is the compound beryllium

part III-6).

care

beryllium

order

(see

for amounts

“basic”

hydroxide

employed

analyses,

for

although

330° ) permits

the

its isola-

tion by distillation. The

second

which possess prepared

group

of chelate

a negative

charge.

with a number

citrate,

$alicylate

and sulfate.

phase

Complex

formation

ion exchange analogues

in a solvent

Details involving

procedure

of this type have been including formed

oxslate,

malonate,

with oxalate

acetylacetone

from

for berylli~m.

has the

23

has been demonstrated and used in the 24 The sslicylate of the group II metals.

separation

of beryllium 26

and gentisic

25

of the solvent chelate

complex

of beryllium

extraction

have been used as completing

of berylllum.

The

anions

are those

with citrate

sulfosalicylate

separation

of beryllium

Complexes

of complextig

been used in the back-extraction orgsnic

complexes

complexes

agents

acid (2, 5 -dihydro~lbenzoic in an ion exchange

snd for the spectrophotometric

extraction

and ion exchange

of beryllium

and -7.

‘7

will

procedure

acid) for

determination

procedures

be outlined

in parts

IH -6

4.

Soluble

Beryllium salts

Compounds

hydroxide

are extensively

probably acids

also

water.

is a weak base

hydrolyses,

colloids

as HCN,

adsorption

O. i M NaCl was varied on glass

(BeO)x

of beryllium

buffered

containers

solutions

observed

k

to the absorption Figure

carrier-free

solutions

in 2

of pH.

Absorption

as high as 20~0

at the higher

of

i shows the

as a function

of HC1 or NaOH.

were

of its

hydrolyses

leads

vessel.

with O. 00i M NAc

by addition

completely

of the containtig

of Be 7 from

solutions

ions like Be(OH)+ and ++ Be . Salts of such weak

HZS and H2C0 ~ are almost

onto the walls

percentage

and therefore

forming

of the form

The hydrolysis

beryllium

of Beryllium

The pH

pH ts.

40 30 -

GLASS

20 -

/#f

100

*A

POLYETHYLENE -

/.-Q~4

3

, 7

6

5

9

e

PH Figure

i.

Beryllium

Adsorption

of beryllium

on the walls

and glass

vessels

solution.

Data of reference

salts

of strong

as a function

mineral

of polyethylene

of the pH of the

2.

acids

such as HNO ~, HC1, HBr,

etc are all quite soluble in water and the salts themselves ‘c104’ ‘2s04’ are usually hydroscopic. The strong tendency of beryllium to form complex from

ions is shown by the fact that these

aqueous

beryllium,

with at least

corresponding

Soluble

complex

been mentioned The action insoluble

solution

to the tetraaquQ

III-2

of strong

Be(OH)2.

4 molecules

ions with F- , oxalate,

(parts

aq,

tated beryllium

hydroxide

of water

crystallize per atom of

complex. citrate,

such as NaOH

but addition

At room

always

etc.

have already

and -3).

bases

to redissolve.

salts

of excess

temperature in O. 39 N,

or KOH first base causes

the volubility

the precipitate

of freshly

O. 65 N and i. 99 N

8

precipitate

precipi-

NaOH

is

reported The

to be O, 06, 0. i44 and O. 66 moles

solution,

beryllium

however,

is unstable.

is reprecipitated

pondtig

to the formula

hydroxide

is a very

whenever

a strong

of insoluble, subjected

useful base

the opposite

Insoluble

The most

boiling

separations from

amphoteric

nature

precipitant

for beryllium

The precipitate is essentially

of the freshly

insoluble

properties

carbonate

boiled.

In this case

basic

beryllium

Addition

the basic

tendency

of the weakness

nature,

Ignition

chemistry.

precipitate

of the precipitate

(NH4)2HP04 results

of beryllium

9

also or

strong

the phosphates

of

At lower

pHrs soluble

insoluble

precipitates

pHls

to identify,

are formed.

approximating

to beryllium

in Be2P207.

of

oxide.

compounds,

crystalline

is

precipitate

and the consequent

difficult

by adding

solution

of the hydroxides

in beryllium

at higher

if the

composition.

Ignition

and therefore

an insoluble

may be obtatied

while

28

Xl&dine

is obtained

granular

to a solution

of the acid,

complicated

may be obtained,

of gelatinous

results

of the resulting

have a rather

compounds

solution

pH 5,

with the amphoteric

indefinite

carbonate.

carbonate

to hydrolysis

beryllium

However,

beryllium

beryllium

Because

of somewhat

boilhig

carbonate

a white,

ion.

Precipitation

result

in ammonium

bicarbonate

at around

from

in connection similar

with ~4+

IEM been recommended.

Be(OH)2

is obtainep

carbonate

basic

to appear

of the

the beet

buffered

of this reagent.

A somewhat

of beryllium

of sodium

precipitates

above

It is

Because

hydroxide

unhydrated

there

lest

so far as

hydroxide,

red end point (pH -6)

of beryllium.

complex

of the beryllium

base.

precipitated

in an excess

has been mentioned

should not be

of beryllium,

by dilute

which begins

of dense,

a mixture

is the hydroxide.

is ammonium

at the methyl

Precipitation

compound

solution

of beryllium,

from

but

of Beryllium

is concerned,

aqueous

-

of beryllium

separations,

beryllium

solution

corres

be obtained.

insoluble

precipitated

of beryllium

result

nature

the mixture

to effect

Compounds

important

radiochemical

solution

hydroxides

or on boiling,

precipitate

in radiochemical

is used to dissolve

of the desired

5.

crystalline

27

per liter.

standing,

The amphoteric

property

non -amphoteric

to prolonged

On long

as a dense

Be(OH) z.

of Be(OH)2

This

NH4BsP04

solutions procedure

at pH 5.5. is

29

therefore

useful

in obtaining

beryllium

in a dense

form

of known

c opposition. Another

method

advantages

over

for precipitating

the others

beryllium

involves

which has some

formation

of the BeF4=

complex

by the addition of excess anion by addition of excess F - ion, followed ++ ion Ba. The solution should be acidified and only a slight excess ++ ion should be used in order to prevent the precipitation of of Ba BaFZ.

The resultant

and very

difficult

to filter

Digestion

paper.

somewhat,

completely

through

others

through

mentioned hazard

for

precipitate This

associated

which tend” to “dust”.

more

redissolved

a mixture further

of H3B03

chemical

contaminants Beryllium

processing

tend to co-separate moderately containing extent.

acid.

beryllium Particularly

such as those

useful

of aluminum

for beryllium

precipitate

by treatment Solvent

The chelate acetic

*

acid,

Obtainable

solutions,

complexes

which were

from

where

unwsnted

in

radioactive

that beryllium

which

co-precipitate

and iron. allows

and the insolubility

means

in this respect

mentioned

Massachusetts.

10

the beryllium

to some

hydroxides

as the co-

to be recovered

from

or by other

the

means.

Compounds

with acetylacetone,

in part

Filter

h a solution

solution,

of Beryllium

,of krylJium

is formed

Fe(OH)3

the beryllium

will

is not at least

are gelatinous

Using

with cold NaOH

the M~pore

property

when the solution

will

Extraction

di;solved

hydrolysis,

any precipitate

at pH-7

precipitant

6.

neutral

Almost

easily

to remove

toward

on precipitates 29

being

is much

sample.

tendency

h near

beryllium

precipitate

is a useful

is needed

as do the

in eliminating

of ignited

BaBeF4

BeO,

TMs

a beryllium

1s strong

of its hydrotide

than ignited

and HN03.

from

The

The compact,

ignition

advantage

with the transfer

to filtra-

filters.

does not require

precipitates, readily

prior

filter

can be overcome

Millipor~

is a distinct

is ftie -grained

of dense

i O minutes problem

the use of RA -type

above.

BaBeF4

the usual @pes

but the filtration

and anhydrous

the health

of insoluble

of the precipitate

tion helps

dense,

precipitate

III-3

above,

Corporation,

TTA,

and

lend themselves

Watertown

72,

to very

useful

be given

solvent

in detail

extraction

procedures

for

beryllium.

These

will

below.

Ace~lacetone: By shaking

or stirring

aqueous

pH 4.5

- 8 with ace~lacetone

soluble

in organic

of acetylacetone quantity

other

solvents.

solvent.

5 minutes, longer, beryllium

hastens

of beryllium

carrier-free

acetone,

metal

tracer

or

contatiing for for

20 minutes

i 00~. of the 29

Bolomey

23

and Broido

with 25 ml of a solution

at pH 6 for

2 hours

was extracted

ions likewise

into CC14,

containing

and

into the

Fe,

and Cr,

CHC13,

from

and the divalent

Ca and Mg.

When excess

into the organic

solvents

which were

and iron

acetylacetonates organic

aqueous

phase.

studied.

phase

with acidified of appreciable

containing water

Fe,

was present

CC14 proved

Ni,

specific

of beryllium alcohol EDTA

Mn,

Zn,

Cd,

only beryllium

ammoniacal

solution

aluminum

be extracted.

beryllium

acetylacetonate

may be

unwanted impurities without 23 of beryllium . About 2 drops of

makes

a satisfactory

wash solution

for

this purpose. The beryllium the beryllium

acetylacetonate

back extracted

complex

into water 11

was

to be the best of the

to remove

amounts

O. i N HC1 to 25 ml of water

containing

ions of Co,

slso

more

and isoamyl

solutions

In strongly

could

many of them would

the extraction

alcohol

EDTA

with ace@l-

the extraction

studied

bu~l

chelates

above

makes

and GHmlo30

ace@lacetone

form

described

The use of EDTA

acetylacetonate

the loss

in benzene

and under the conditions

~arin

washed

into benzene

and stirring

phase.

of the activity

for beryllium.

The

of the chelate

at pH 4.5,

20 ml of benzene

beryllium

many other

also be extracted.

extracted

a�s olution

phase.

A great

Cu,

which is

with 4 ml of acetylacetone

to the organic

found that all but a trace

and Al,

the formation

a solution

at

The use of a smti

may be extracted

25 ml of 10~0 acetylacetone

organic

is formed

and Chen found that essentially

is transferred

contahing

complex

beryllium

pure acetylacetone,

Ey stirring

and then adding

Toribara

contatiing

or CC14 may be used.

which the complex

about 1 microgram

Pb,

Either

in benzene

after

suitable

shook

a chelate

of pure acetylacetone

complex,

solutions

may be decomposed

by shaking

the organic

and phase

containing

the chelate

complex

oxalic acid or 6 N HC1. tracer

with equal volumes of either f 0% 23 report that 9670 of Bolomey and Broido

beryllium

Toribara

is back extracted in 2 hours under these conditions. 29 report that i 5 minutes stirring of the organic and Chen

phase with 5 N HC1 is sufficient aqueous phase.

Because

acetylacetonate,

acetylacetone

100–

to transfer

of the volatility

the beryllium

of carrier-free

which dissolves

to the beryllium

in the acid used to

—

Pti6.72

80 -

60 -

40 -

20 .

120

60

Figure

2.

Rate

of extraction

different

back -extract

240

of Be by O. 04 M. TTA

pH values.

reference

180

Data of Bolomey

should be extracted

aqueous phase may then be evaporated If oxalic acid is used to accomplish

carrier

during evaporation

and Wish,

from the aqueous phase

by washing the latter with one or more portions

beryllium

at

3i.

the beryllium

it may be sublimed

in benzene

of fresh benzene.

to dryness

The

under a heat lamp.

of beryllium 23 under a heat lamp without 10SS of activity. With

present

the back -extraction

the loss of beryllium

through volatilization

of the aqueous phase does not appear to be a problem.

o!-Thenoyltrifluoroacetetone: Thenoyltrifluoroacetone many metals,

(TTA)

is a useful chelating

including beryllium.

agent for 31 and Wish have inves -

Bolomey

, Cu++ PH 3.40

100-

g ~. _ 1V u a K% 60 w

1Z w Q a 40 w a FeIU pH 6.38

20 .-

Al PH 3.4 60

Figure

3.

TIME

(MINUTES)

Rate of extraction

of various

in benzene Wish,

tigated the conditions

at different

reference

, 240

180

120

metallic

pH values.

ions by O. 0 i M TTA

Data of Bolorney and

3i.

under which beryllium

may be separated

from

a number

of other metal cation~ using this reagent.

‘I’he compllex

is rather

slow to form and to decompose.

2 is shown the

rate of extraction pHls.

of beryllium

The optimum

extraction

being essentially

of iron (III),

in benzene at different aluminum

aluminum

pH values

is also extracted

of iron is relatively

by O. 0 i M TTA

pH for the extraction

of beryllium

The extraction

In Figure

The back -extraction Sr and Y from benzene

seems

to be about 7, with

complete

in about 3 hours.

and copper by O. Oi M TTA

is shown in Figure

quite favorably

much less of TTA

in benzene at different

favorable complexes

Evidently

at pH 7, but the extraction

at the higher PH. of Be,

Al,

solution made O. 0 i M in TTA

13

3.

Ca,

Fe,

Zn,

by concentrated

TIME (HOURS) 4.

Figure

Back extractions concentrated Wish,

hydrochloric Zn,

and beryllium

a matter

exhaction

or micro

amounts

loss

TTA

Acetic

and

“complete”

(cf.

Section

method

acid to i part

of beryllium.

over

volatilization

of beryllium

Procedure

using TTA For

Fe,

6 hours,

back -extraction.

formic

VI,

of Ca,

requires

i2).

works tracer

in

equally

well

for

concentrations

acetylacetone

that there

of the beryllium

- TTA

of

is no complex.

acid.

When freshly to dryness acetate

through

Aluminum

the back-extraction

has the advantage

of beryllium

Data of Bolomey

Back extraction

concentrated

HC1 accomplishes

solvent

beryllium

for

80 hours,

of a few minutes

The

4.

ti i5 minutes.

the use of 2 parts

concentrated

tracer

at least

acid.

ions with

35.

reference

Y is complete

metallic

hydrochloric

acid is shown in Figure

Sr -d

However,

of several

several

is heated

Be40(0-C0. substance

precipitated timee

beryllium

hydroxide

is evaporated

slowly

32

with glacial acetic acid , or when beryllium 14 , there is formed the chelate compound

to 200° C

CH3)6, insoluble

“basic”

beryllium

in cold water,

acetate.

but readily

14

It is a crystalXne soluble

ti most

common

organic most

solvents

commonly

followed

This

the procedure

7.

Separation

alone.

may be accomplished of the chloroform

acetate

by heating

exchange

with

the-

by the specifici~

25 mtiutes

complex

of ion exchsnge

III and discussed

from

h several resin

in detail

other

cation

of

formation

makes

techniques.

These

below.

Dowex

resin

of i. i M HC1.

At a flow

will

these

volumes

exchange absorbed

rate

owing

pass

a Dowex

of i resin

conditions

eluted

50 column,

volume

with 6 or 7 resin begins

to elute

of i. 1 M HC1 have been passed

through

Dowex

50 resin

members

have used

and Grummitt34 to effect

of the slkaline

a separation earth

5. 35 Honda and Kakihana36

aluminum

i. 5 M HC1 as eluting of beryllium

family.

Their

from

results

agent

snd

the other

sre

shown in

Figure

from

Dowex

cations

50 resin

displace

h

have investigated

by the use of dilute from

and

of eluent

the column. Milton

to

slowly through 28 passed a and Kohman

was completely

Under

i 2 to i5 resin

is strongly

Be and Al through

the beryllium

by cation

50 at pH 6 - 8, presumably

pHfs beryllium 33 solumn . Ehmann

containing

species

Beryllium

ways.

At lower

it with i. i M HC1.

only sfter

is somewhat

somewhat

toward

by a varie~

exchange

f or-mation2.

volumes

of other

Resins:

i. i M HC1 solution

per

free

of Beryllium

of beryllium

of beryllium

on the cation

followed

acetate

is offset

Behavior

in Table

accomplished

a cation

solution

beryllium

beryllium

disadvantage

tendency

Exchange

colloid

of basic

its separation

may &

acetate

with HC1 or with water

chloroform

of the basic

Ion Exchange

summarized

Cation

and may be washed

acidified

tie

beryllium

for beryllium.

strong

possible

of “basic�

is the solvent

HNO ~.

consumtig.

The

Chloroform

HNO ~ or by evaporation

by decomposition

The preparation

=e

from

with reagent

concentrated

stable

with water

of beryllium

by extraction

and ether.

The solution

is remarkably.

by extracting

Recovery

alcohol

employed.

in chloroform cations

except

the column,

16

the elution

of beryllium

Ca or Mg solutions.

which therefore

passes

These through,

but cations earths

such as Al which

are retahed

Completing

are

more

strongly

held than the alkaline

by the resin.

agents,

for either

unwanted

cations

been used in the separation

of beryllium

by cation

Merrill,

have studied

the effect

Table

Honda

ILI.

and tinold2

Ion Exchange

Methods

Cation Resin

Elut.kg

Form

or beryllium, exchange

resins.

of various

for the Separation

have

completing

of Beryllium

Exchange

Agent

Ions Eluted

Ions Retained Al, Mg, Ca, Sr, Ba

Reference 28, 34, 35

m

ca iM HC1

Be

HR

O. 05 M Ca or Mg

Be

HR

O. 4 M oxalic

Al, Fe’+, U02* Th, others

Be

2

HR

oxalic acid pH 4.4-5

Al,

Be

37

~4R

0.55 M bm.lac. pH 5

Be

other

~4R

i

Be

Cu,

Ni

20

Al, Fe3+, Mn++ heavy metals, others

Be,

alk. earths

2, 38, 39

acid

0%(NH4)2C0 ~

35, 36

Fe

alk. earths

34

PH 8. 5-9 pH 3. 5-4.0

NaR

EDTA,

~4R

0.35 M acetate

Be

Al, alk. earths, U, others

2

NaR

acetylacetone pH 5

Be

Al, alk. earths U, others

2

NH4R

0.02 M sulfosalicylic acid pH 3.54.5

Be

Cu,

25

hion RC 204

O. i M oxalic 0.45 M HC1

RCit

acid

U, Ca

Exchange 28

Be

N

i M amm. cit. pH 8

Be

other

RC1

v~ious

Be

many transition elements

40-42

RC1

i3 M LiCl

alk. metals, Mg

Be

43

cone. HC1

16

alk. earths

24

6elo

Io.o ?::

,

I

I

1

maoloo

20 3040 m

I

,

1

1

I

20

ELUATE Figure

5.

The

separation

of berylJium,

and strontium

x 8 cm,

rate

flow

in these

23 - 250 C.

They

1.0 ml/min,

of beryllium

define

which were

the distribution

at equilibrium. distribution

=

coefficient, ++

D= measured

resin.

‘7 Be

MNa+

adsorbedlg

rematiing

Data

34.

50 resin. conducted

coefficient

Be7 was used as at room of Be,

temperature, / Kd, to be

/ ml solution

of normalization

they slso

define

the

resin /ml solution

of complex

agents.

, and with the resin

to be 700 for In O. i M H+,

T w 600 C.

i. i

D, to be

in the absence

In O.i measured

purposes

i. 5 M

/ g resin

Be7 remaining

For

calcium,

50 column

reference

by Dowex

Be7 adsorbed ‘d

using

Dowex

and Grurnmitt,

experiments

magnesium,

exchange

acid eluant.

on the uptake

a tracer

by cation

hydrochloric

of Milton agents

VOLUME (ml)

200-400

in the sodium

mesh

resin

and with the resin

17

form,

and 830 for

in the hydrogen

D was 50-i OO mesh form,

D was

measured to vary

to be i870 for

50-100

with the concentration,

mesh C,

resin.

The

value

of the monovalent

of D was found

cation

and in the neighborhood

of the concentrations which were K Values of the qusntia _ d ~e show-n in Figure as _.i 2 D again% the concentration of completing agent for several Stability these

cation

Because

constants

were

exchange

data and are given

certati

unwanted

than does beryllium, oxalate

calculated

for the several

cations

in Table

may form

the use of completing

can be quite effective

used D varied 6 plotted cases.

complexes

from

I, page 4. much stronger

agents

in isolating

in the, solution,

complexes

such as EDTA

beryllium

from

or

a mkture

1,0(

~J o

0.14

Kd T

x

x

0.0

O.oc

1

t

12

II

I

I

1

lo9e

1

1

I

1

EOlA(Y4-1,0.0SM AC:~N~:ETONC

Na+-Na [A-),

R

0.1 M

❑

.

OXAMTE

+

■

P~SWRIC

● = M = OXALIC

ACID [d),

0.1 M

H+-HN

A

ACFO&),

D. I M

M+-No

Figure

■

OXALIC

6.

Uptake solutions

AGENT

(A=kQl M Hi++aR ACIO (A-)

0.05

HcPOo-(A-l. O.IU N#-Na

M H+-HR R

R

of beryllium contatiing

Data of Merrill,

i

21

-LOG [An-] CONCENTRATION OF COMPLETING 0. ~.

1

1

76543

by Dowex various

Honda,

10

50 resin completing

and Arnold,

from agents. reference

2.

of

cations.

EDTA

separation

of beryllium

small

uptake

Using

Amberlite

Athavsle38

is especially

IR-i20

Oxalic as Fe ‘3,

resin

acid is useful Al+’,

in the sodium

form

containing

If H202

unabsorbed

snd Th+4.

is present.

Nadkarni,

while

in the

lY shows the

EDTA

excess

by the resin

Varde

Na2H2

and

EDTA

aluminum,

was present

2

.

calcium

titanium

also

by the resin.

for the separation

U02+2,

Table

50 when excess

the column.

the column

particularly

and aluminum.

solutions

was absorbed

through

through

iron

in this respect,

by Dowex

found that from

and tion passed passed

from

of aluminum

at pH 3.5 beryllium

useful

of beryllium

used to elute these Ryabchikov

of beryllium

by the use of oxalate ions while

beryllium

separation

of beryllium

from

IV.

Uptake

of Aluminum

Containing

magnesium

by Dowex

Excess

from

Iron and aluminum

is retained

pass

on the column.

and tie

50 from

other

alkaline

Solutions

pH after ~assing

Al absorbed (mmole /g resin)

50

2.79

--

0.19

30

3.10

3. 2i

0.007

30

3.62

3.78

0.003

50

3.52

3.61

0.0026

a Sample

S04=; CaCO

Arnold,

+ O. Oi M excess

0.22MNa++0.iMAlY-

solution:

q added to adjust

reference

tion

EDTA

pH &fore passing

Volume of solu tion passeda

+

at pH 4.4.

as complex

Table

O. 4 M solution,

ions wldle beryllium is retained 37 report the separation and ESukhtiarov

and aluminum

The

acid,

such ions

may be 2 on the column.

through

Oxalic

from

Data of Merrill,

PH.

Honda,

EDTA and

2.

earths

by means of ammonium lactate has been described by Milton and 34 Using O. 55 M ammonium lactate at pH 5 as the elusnt, a Grummitt. flow ature

rate

of i ml/min.

of 78° C,

than 2 interstitial of magnesium,

, and a Dowex

beryllium column

was eluted volumes.

which began to elute

50 column from This

19

at a temper-

a i. i x 8 cm column was considerably

at sround

volumes.

mdntained

2.5 interstitial

in less

h advance column

The use of salicylate adsorbed

for

selective

elution

of beryllium

on a Dowex

50 resin column has been reported by Schubert, 22 Using O. 02 - 0. iO M sulfosalicylic acid at and Westfall. ++ beryllium is selectively eluted while Cu ‘+, U02++ and Ca

Lindenbaum pH 3.5

analogs

-4.5

ions remain column

firmly

on the column.

it can be eluted

before

If iron

is slso

the beryllium

adsorbed

on the

with O. i M sulfosalicylic

‘

acid at pH 2. i. When

acid at pH 6.0 is used to elute a Dowex 50 ++ ++ containing adsorbed Ca ions the beryllium and Be

(H - form)

column comes 1.9,

O. i M gentisic

off in a sharp

band,

beginning

when the pH of the effluent

reaches

reaching

a maximum at pH 2.74 and complete when the effluent 25 pH 5.60. Under these conditions calcium is still retained

reaches

on

the column. Starting Be,

witi

i50 ml of solution

and O. i M in suJfosalicylic

solution

through

a column

passed

of wash solution completely

( >3

~C2.

In

contain dl

passed

the column

the

Dowex

50 resin

acid at pH 4.5.

with the aid of 70 ml

acid at pH 4. 5) while

calcium

was

of beryllium free

adsorbed of unwanted

M) HC1, 33’38’44 latter

the

the beryllium,

on a cation

case

cations

exchange

resin

may be accomplished

or by a solution O. 5 - i. 5 column

of O. 5 M NaAc volumes

which may be recovered

and

of effluent

as Be(OH)2

by

NH40H2. Exc hange Resins:

Anion

The use of anion exchsnge implies

the forination

desired

element

example

to be separated,

Beryllium passing

with chloride 45 I resin. A great complexes

may therefore the solution

h the separation charged

complex

or of unwanted

in hydrochloric

a complex

chloride

resins

of negatively

of the latter,

on Dowex form

through

(O. i M md.fosalicylic

elution

by strong

form

authors

i5 g of air-dried

with O. i M suJfosalicylic

completely

which has been washed

addhg

these

5 pg of

adsorbed.

Rapid

1 M

i. i g of CaC12,

acid at pH 4.5,

containing

which had been equilibrated Beryllium

containing

many other

in hydrochloric

of the

As am does not

to be absorbed

from

ions do, however, 40-42 by Dowex I resin.

these

elements

acid of appropriate

20

either

berylMum

strength

cations

metal

which are absorbed be separated

ions,

impurities.

acid solution

ion of sufficient

of metal

by simply

strength

through

a Dowex

beryllium

will

Even from

I resin

column.

pass through

shows negligible

i2 M HC1 solutions, from

(Be adsorbed

of solution)

beryllium

absorbable

elements

,hion negative used,

adsor@ion

per Kg resin/Be

could be separated such as alkali

exchange

be adsorbed

while

onto Dowex

I resin

it is interesting that there is adsorption of 43 solution. With a distribution coefficient of

i 3 M LiCl

8 in this solution

ions will

umdsorbed.

though beryllium

beryllium

Unwanted

separations

remaking

per liter

by anion exchange

metals

and magnesium

of beryllium

based

from

non-

by this technique.

on the formation

of

complexes

of beryllium do not appear to have been extensively 28 have used the oxalate complex of and Kohman

EhmamI

beryllium

to effect

chloride

radiochemical

solution, -0.

‘2c204 column

after

evaporation

I resin

solution,

which

at a flow

rate

effected

of beryllium.

to dryness

i5 M HC1 (pH = O. 9) solution

of Dowex

the same

purification

was taken up h

and passed

of i ml /min.

the eleution

BerylJium O. i M

through

a 4“ x i/2°

Elution

was by

of beryllium

in 5 resin

volumes. Nelson elements

and Kraus

studied

by anion exchange

Beryllium fam~

24

is more

at low citiate

greater

the separation

using

strongly

citrate

absorbed

concentrations,

than about O. 1 M magnesium

beryllium.

Effective

separation

is more

strongly

is less

Using

but the last portion

Alternatively, first

but tails

using badly

from

of the

coricentrations absorbed

Ca,

Sr,

but the separation

will

from

and contaminates

the beryllium

magne 13ium

comes

be contamtited

O. 2 M (NH4) 3Cit at pH 4.3 magnesium

than

Ba and Ra

i M (NH4) 3Cit at pH 8 beryllium

of beryllium

I resin.

members

at citrate

of beryllium

earth

and Dowex

although

by this technique,

first,

solutions

than the other

may be accomplished satisfactory.

of the alkaline

off

with magnesium. comes

as it is eluted

off from

the column.

IV.

PROCEDURES

COMPOUNDS

Inasmuch nitrate,

FOR DISSOLVING

SAMPLES

CONTAINING

OF EERYLLIUM

as the common

sulfate

salts

etc. , are freely

of beryllium,

soluble

21

in water,

the chloride, the problem

fluoride, of

dissolving

the sample

is that of rendertig

in which the berylJium metal

itself

metal

also

the best dissolves

character

are hydrochloric

in alkali

hydrotide

material

solvent

aqua regia

acid,

content

is the solvent

sample.

a _

At the same should

ensure

time

before

ion is sidkr destroying

proceeding

h behavior the BeF4=

bulk of the fluorides

complex

anion.

is to treat

iron

meteorite

For

siliceous

from

the

with

However,

fluoride care

and the beryllium The BeF4 = complex

with the separation. to the ~4=

For

a complex

exchange.

the fluorides,

sediments

is volatilized,

component

forms

good carrier-tracer

should be taken to decompose complex,

the silica

the berylJium

or dilute,

passive.

employed.

troublesome

The

to the amphoteric

and of various

commonly

and otherwise

acid.

to the geochemist.

solvent;

material

of befyllium

concentrated

of meteorites

HF is the appropriate

eltiinating

either

owing

the metal

interest

case

or sulfuric

solutions

for it renders

is of considerable

materials

which

Nitric

the matrix

the special

solvents

The radioberyllium and rocks

For

is tibedded.

of the element.

is not a suitable

soluble

The best method

the sample

have been decomposed

for

with HBO ~ after

by treatment

the

with HNO ~ or

H2S04. Because

of the formation

use of a NaF

fusion

has been reported

V.

COUNTING

counting

to render soluble 19 by Rural .

TECHNIQUES

emitted

counting

the beryllium

FOR USE WITH

in N

is the obvious

radiation

choice

for

that other

which would give

rise

to O. 54 Mev

in the sample

the counting

present

in siliceous

ISOTOPES

the samples

OF BERYLLIUM

from

In addition

Be 7 is a y ray of O. 477 Mev (see

detection

y-emitting

only if a y ray spectrometer spectrum

from

ii?~. of the decays

of the possibility

beryllium

ion with fluorides,

of Be 7

The only observable ener~

complex

of BeF4=

Part

U).

Scintillation

of these

species,

annihilation

y rays. Because + or ~ -emitting species

quanta,

might

be

of Be 7 can be done with assurance

is available

for examihing

the y ray

the sample. to the criterion

sample

for counting

of radiochemical

puri@p

i. e. the

must show only a O. 477 Mev

22

y ray,

one may also require that the sample 7 since Be emits none. In particular} is produced

in nuclear

Part 11, production these instances

reactions

emit no particle

this is a requirement

in the laboratory.

of (3-emitting

40

Be

radiations.? when Be 7

44.s discussed

in significant

intensities

in in

is negligible.

For the study of Be 7 produced in nature i6-4,8 by cosmic ray action, Be is also known to be produced so itl -that a low intensity of (3 emission from Be is to be expected.

40

A third criterion is the half-life Because

of the radiochemical

for decay of -the samplet

desirable

particularly

to establish

sample

which should be 54 day.

of the long time lapse required

this magnitude,

purity of a beryllium

to establish

for samples

the radiochemical

a half-life

of low activity,

of

it is generally

purity of the sample

by other

means. Where species

other means

are lacking?

of establishing

the constancy

rate per mg of sample) radiochemical that the activity

the intensity

with the element

for beryllium

of the specific

the identity of the activity have

of the sample,

to obtain an accurate

fall back on the constancy

a very reliable

in order to minimize

of

to demonstrate

the presence

of 30 c /m or less,

detect low intensitiess or particle-emitting

must therefore

(counting

of

pure condition in a counting sample

is very 10W9 of the order

it may be very difficult

establishing

sufficient

situation for establishing

Be 7 in a radiochemically

activity

when put through a number

steps is usually

is isotopic

The most difficult

of the specific

of the sample

purification

the identity of a radioactive

arises

in which case

y ray spectrum

impurities. activity

or to

One must then

as a criterion

for

which is being counted.

and specific

One

radiochernical

the possibility

when

procedure

of having a. radioactive

contaminant

in the counting sample. Enthis regard it is worth drawing 202 ~ which decays by K and L capture to to the nuclide T1

attention 202 with the emission Hg close

Mev

to that of Be 7 that the chance

nuclear

reactions

The closeness quanta makes rates

of 0.44

on mercury in energy

rather

of Be 7 samples.

y rays.

of producing

and lead isotopes of the y ray

Solutions

this species

23

by

annihilation

of absolute

of the (3+-emitting

standardized

is so

should not be overlooked.

of Be7 to O. 5i Mev

easy the determination

which have been accurately

Its y ray energy

disintegration 22 species Na

for their absolute

specific

activities

are

Provided

the source

rate

of emission

positron

is sufficiently

rate

quanta,

efficiency

which will

this y ray will

energy

to those

this Mficul&

arising

counting source

rate

within

in the enerw

is first

counting

rate

counting

rates

2 tich

well-type

from

way.

measured

using

a rather

entirely

quanta to the counting

rate

efficiency

below

of This

which can

window

to obtain the

two regions.

to the counting

detector

between

rates

the O. 51 Mev

due to i. 28 Mev

by interpolation

scintillation

to get around

The counting

small

width in these

the contribution

of the O. 5i Mev photopeak

In order

in

to the observed 22 the 1.28 Mev y ray of a Na

and a little

be used to estimate

equivalent

Contributions

above

be almost

somewhat,

with a window

a little

will

efficiency

of the O. 5 i Mev photo peak.

in the following

per unit window

for

matters

the detection

spectrometer

this window

region

pulses

quanta.

to determine

the photopeak.

may be estimated

photopeak

O. 54 Mev

a scintillation

to straddle

detector

to the detection

to some

in the neighborhood

done using

be opened

rise

the

may then be used to

of the scintillation close

the

be just twice

y ray which complicates

give

from

purposes.

quanta will The source

be very

it is necessary

the stint.illator is best

also

calibration

thick to stop all positrons,

anntiflation

O. 477 Mev quanta. 22 has also a i. 28 Mev Na

since

for

of the source.

the detection

O. 5i Mev

available

of O. 51 Mev

emission

determine

for

commercially

These

rate

in the region

them.

the contribution

and can

quanta,

In a typical

from

h the O. 5i Mev photopeak

1.28 Mev

amounts

to about

i 7% of the total. Having fall

established

within the window

of the spectrometer is given

=

of annihilation the detection

straddling

quanta which

efficien&,

the O. 5i Mev

E,

photopeak

~.fa emission

for absorption

correct

the source

Na22

R,

of the spectrometer,

with the window

D is the position

be made

rate,

by E

to

the counting

sample

of the source

of O. 51 Mev

is not too thick,

to cancel

rate

a similar

quanta withh

fa is not a very correction

is about the same

thickness

24

and fa is a factor the source.

significant

factor

factor,

for beryllium

as the beryllium

Provided and can

if the samples.

Having determined O. 54 Mev quanta, an appropriate

the counting efficiency

the base line of the spectrometer

for

is shifted downward

amount so that the window of the spectrometer

the O. 477 Mev, photopeak of Be7.

of the spectrometer

well -type scintillation

photopeak~

in which case the detection

is very close

detector

straddles

The same window width should be used

as for the O. 5 i Mev annihilation efficiency

of the scintillator

to E.

For a typical

2 inch

E has a value of about 6 percent

for

O. 5 Mev quanta. Restricting

the energy

interval

in which pulses

the photopeak re suits in an appreciable

loss

wili be counted to

in counting rate of the

source

over that which could be obtained if a window were not used. 7 rate of the source could be strong Be source the disintegration

determined

as outlined above and the sample

counting efficiency a minimum rates

because

for sources

of a few hundred counts per minute.

howeverp ii results

favorable

above

with counting

With very weak

counting with a window is usually in a more

the

counter which counts all pulses

This is satisfactory

threshold.

in excess

sourcesj

of a scintillation

used to determine

With

to be preferred

sample -to -background

counting

ratio. Counting of Be Because likely

40

of the long half life of Be

to be of importance

10

~ and the fact that this nuclide

only in nuclear

reactions

produced

through

is the

action of cosmic rays, the disintegration rate of any sample containing $0 will be very small indeed. When the low p decay energy of Be 40 becomes a formidable O. 555 Mev is considered also, the counting of Be task.

Evidently

Geiger

some type of low level Since procedures free amounts, Presumably beryllium

counter

is called

are available

counting samples the thickness

counting

in

for.

for isolating

of the final sample

separation

of thin samples

beryllium

in carrier-

which are very thin can be prepared.

content of the starting

such a carrier-free of Be’”

or proportional

material

is limited

which is analyse d.

were attempted

could be obtained by measuring

which was added at the beginning

by the

the recovery

the recovery

of the analysis.

If

of a Be

Of course

efficiency 7

“spike”

the amount

of Be 7 spike to be added should be chosen so that its counting rate does 10 not overwhelm that due to Be . The much lower counting efficiency

25

of Be7 y radiation

in a Geiger

roughly

the disintegration

i 00 times

may be present

or proportional

in the sample

rate

before

counter

means

of Be 7 compared

the accuracy

that

with Be

of counting

io

of

i8 impaired.

Beio

The identity of beryllium

of Be

rate

from

the carrier-free

in a manner

ia present.

on the sample,

to that which is 10 of the ratio of the Be

, when repeated

should

suffice

separation

similar

The constancy

to that of Be 7 tracer

are performed 13activity

in a sample

could be determined

used when carrier counting

10

chemical

separations

to demonstrate

that any

is due to Beio.

Because be required condition,

of the complexity

of the chemical

in some

for

instances

or in high yield,

carrier.

In this case

appreciable

beryllium

it may be necessary

the final

thiclmess,

isolating

separation

sample

for

and the countig

which may

in a pure

to add beryllium

counting

efficiency

will will

have an be somewhat

impaired. Two

systems

for

been described. counter

The earlier

of the type

The beryllium

described

counting

hemi-cytiders

The hemicylinders thin wall counter.

rtig

However,

is mounted from

To reduce

under these correction

for

purity

to calculate

the self

radioactive

species.

contact with the

the geometry

Because

conditions

the sample

self-absorption

from

in alcohol.

of the counter

the counter is surrounded

by the method

of the radiations

46

wsJls of two

of the sample

counters.

Figure 7 shows an absorption 10 using such a counter. from Be

on the radioactive

a slurry

background

and Libby.

on the inside

Under these conditions

and may be determined

curve

Wolfgang

are then placed in close

of anti -coticidence

quite large

by Sugihara,

sample

by deposition

is about 40%.

io moderately thick Be samples have i6 uses a thin wsJl cylindrical of these

counting

the sample

can be made

of the radiations

of the sample,

sample

serves

can be

quite thin. is necessv,

of Suttle and Libby.

curve in polyethylene i6 The measurement

a beryllium

area

by a

47

of the radiations of the absorption as a check

and the data may be used

absorption of the radiations by the sample, 28 Ehmann and Kohman have recently described a counting procedure io for measurhqg very low levels of Be and other naturally -occurrtig They

use a side-window

26

counter

having

a window

la ,

Y

z > . *~ 10> G

SAMPLE TNICKNESS (m@cmt]

Fig.

8. Relative

counting rate per

unit weight of sample for samples

I

10 m3040

o

so

ABSORBER THICKNESS

60

of Be10

fixed

(mq/km&)

specific

the sample Fig.

Absorption

7.

curve

polyethylene

of Bel 0 in

in close

geometry.

Arnold,

vs.

thicknesses.

Data of Ehmann and Koh-

Data of

reference

activity

cylinman,

drical

in BeO of

70

reference

extrapolation

16.

thickness

The

28.

to zero

was made from

data of Nervik

and Steven-

son, reference

47.

-1

area

slightly

counters. counter

over The

6 cm~,

sample

h a geometry

to construct

with a surrounding

is placed close

and operate,

be quite so thin as in the thin wall self

scattertig

of self

in moderately

absorption

in a dish close

to 40Y0.

although

shield

This

counting counter

thin samples

as shown in Figure

8.

27

to the window

system

is ~erently

samples described helps

of anti-coincidence

will

of the simpler

generally

above.

to overcome

not

However, the effects

VI. FOR

COLLECTION

OF DETAILED

RADIOCHEMICAL

PROCEDURES

BERYLLIUM PROCEDURE

Separation Source

of beryllium

- W. D. Acts

~

stone mete orite

from

Ehmann

i

and T.

material

Kohman,

Geochim.

et Cosmochim.

with acetone

to remove

any laquer

P:

340 (i958).

Procedure:

s“

Rinse

the specimen

may have been used to preserve Step 2.

Grind

a 50-i50

g sample

using

an electrolytic

this fine pow”der to a i placed

Y!%@

h a waterbath

Dissolve

the sample

48% hydrofluoric

it.

of the specimen

iron

sheet

liter

to a find powder

and iron

roller.

polyethylene

at room

Transfer

beaker

which id

temperature.

in a hood “by the cautious

acid.

which

(Note

i)

additicm

of

“About 5 ml of bydrofluoric

acid per gram

of sample

is used.

stand at room

temperature

for

Allow

the mixture

to

with occasional

3-4 hours

stirr irig. Heat the mixture stirring,

on a water

until the mixture

of HF to the residue 50 ml cone. Dissolve

HN03

HC1.

Add =

through

residue accurately

and transfer

with occasional

just to dryness. evaporate

iron -d

Add

to dryness.

again

reduce

to dryness.

HC1 and again

to remove.

HF and HNO ~.

excess

from

a funnel with fritted

the solution

in i 1. of 9-i O M glass

carrier

to a 2 1. se,paratory

28

disk to remove

found in trace

known amount of &

Repeat

HC1.

the evaporation

which is usually

50 ml Add

in iOO ml of cone.

witi” i 00 ml of cone.

the residue

Filter

‘tisoluble

to oxidize

to dryness

the evaporation

goes

and again

the residue

evaporate

Dissolve

bath at i 00° C,

~ount. to the solution

furmel.

.PRocEDuRE

Extract ether

which has been satimated are usually

extracts

three

the washings Reduce

times

the volume

approximately

sufficient,

resin.

rate

Reduce

the flow

Filter

phase.

Pass

maktig

the solution

X-i

Dissolve

*

Transfer

filter

paper

a Millipore

as in Step 9.

-

h dilute

Repeat

carrier.

combining

to precipitate *

Al(OH)s

Filter

off the precipitate

dilute

HC1.

methyl

red end point.

Step i4.

Dissolve mount

water

and time.

on the filter

slurry

through

a

‘

of hut water, the solution

the solution

at the methyl

with

them

with NH40H

the precipitate

6 M HC1

red end pofit.

and redissolve

in

at the

and again repeat

red end pokt.

Al and Be hydroxides

to approximately

and heat

amount Dilute

the hydroxides Filter

paper

10-20

disk.

and treat

d hydroxides

of 6 N HC1 nece sssry

the solution

glass

and Be(OH)2

at the methyl

the precipitated

a third

the filter

with the filtrate.

Reprecipitate

the precipitation

HC1 and reprecipitate

the warm

funnel

to pH 7.

in the funnel with a small

to 250 ml with distilled

2)

the eluates.

Add 25 ml of 8 M NaOH,and

Filter

the washings

(Note

in a 6.5 cm Buchner

the precipitation

a 6.5 cm fritted

Wash the solids

ion exchange

Al and Be hydroxides.

Macerate

to boiling.

c ontatiing

1 ml /mti.

Al and Be hydroxides

to a 250 ml beaker.

funnel having

an

to 300 ml on a hot plate.

HA fflter

the precipitated

the m&ture

through

to approximately”

of the solution

the precipitate

mg of Fe (~)

the solutibn

O, 100 - 200 mesh

and wash with 25 ml of 5% NH4C1 adjusted Step 10.

combining

to about 250 ml on a hot plate.

to pH 7 to precipitate

through

ether

with 500 ml of i O M HC1 and combine

the volume

Add NH40H

of four

approximate ely 2.5 cm’ in diameter i,

W&mh the column

Three

of 9 M HC1,

add 500 ml of i2 N HC1,

200 - 250 ml of Dowex Adjust

aqueous

of the solution

column

of isopropyl

Wash the combined

with 50 ml portions

10 M in HC1.

ion exctige

ml portions

with 9 M HC1.

with the extracted

To this solution

!WE!&

300 -400

iron with consecutive

extraction

Step 8.

1 (CONTINUED)

to yield. complete 50 ml with distilled

in the minimum solution. water

Dilute and

PROCEDURE

Step 15.

adjust the acidity

to i. i M HC1 by dropwise

using

a pH meter

and standard

Pass

the solution

X-8,

50-100

diameter After

through

mesh

ion exchange

the solution

usually

column

has passed

through

the effluent

Dissolve

conttiing

the residue

through

long and i/2 in.

for

rate

(Note

elution

i ion exchange

h diameter.,

After

is washed

washing

is added to the first

is

eluted,

3)

Be to dryness”

a 5 ml Dowex

the column

50,

to i ml /min.

on a steam

in 25 ml of 2 M HC1.

solution

comparison.

about i/2 inch h

the column

volumes.

of 6 M HC1,

of Dowex

with i. i M HC1 until Be is completely

Evaporate

solution

volume

.4djust the flow

in about 6 or 7 resfi

bath.

addition

1. i M HC1 solution

a 25 ml resin

snd 10 in. long.

continued

Step 16.

1 (CONTINIJED)

Pass

column

passage

the 2 in.

of the sample

with 10 ml of 2 M HC1 and the +2 is adsorbed in eluate. Pb

the column. Step i7.

Evaporate Dissolve

the eluate the residue

(PH = O. 9). column rate

Pass

Treat

precipitate filter

precipitate

-

volumes

through

Be(OH)2.

paper

yield,

5 resin

from

solution

elution

- i. 5 M HC1

&ough

a Dowex

in a 6.5 cm Buchner at i OOO°C, weigh

and mount the sample

50 ml)

passes

with NH40H

funnel,

Al is

through. to pH z 7 to

on Millipore Ignite

counting.

(Note

HA

the

the BeO to determine for

-

of the eluting

Residual

the precipitate

i

at a flow

O. i M H2C04

(about

beryllium

the column Ftiter

with

the column.,

on the ,column while

the eluate

to dryness.

and i./2 in. h“ diameter

Continue

has passed

adsorbed

Recycle

the resulting

of i ml/min.

solution

the be~llium

in 25 ml of O. i M H2C204

4 in. in length

0.45 M HC1 until

Step i8.

containing

a chemical 4)

Procedure: Transfer treat

the BeO from

it with a mixture

9 M H2S04.

Boil

the counting of 45 ml cone.

the mixture

30

tray

to a beaker

13N03 ~d

on a hot plate

fbr

and

i5 ml i hour,

or

~,

PROCEDURE

until the solution ml with distilled Step 2.

Add about

I (CONTINUED)

is complete.

Dilute the solution to iOO

water.

10 mg Fe (III) carrier

tate Fe(OH)s precipitate

and Be(OH)2

to the solution

with NH40H

on Wha’cman No.

3i filter

and precipi -

at pH ~ 7.

Filter

paper in a 6.5

cm

the

Buchner funnel. Step 3.

Transfer

the filter

paper and hydroxides

to a 250 ml beaker

and treat with i5 ml of 8 M NaOH solution. to boiling and filter a 6.5 cm fritted

the warm

glass

disk.

slurry

Dilute the combined to precipitate on Millipore Dissolve

solutions

at pH w 7 to assure Step 5,

?lissolve

the final

column

Filter

removal Be(OH}

this precipitate

cm Buchner funnel.

and reprecipitate

twice with NH40H

of the Na+ present.

z precipitate

HC1 and pass the solution exchange

to iOO ml and add 6 M HCI

paper in a 6.5

the precipitate

with 10 ml

to the filtrate.

13e(O_H)z at pH w 7. HA filter

through a funnel having

Wash the residue

of 8 M NaOH adding the washings Step 4.

Heat. the solution

through

in 25 ml of cone.

a iO ml Dowex. i anion

4 in, long and 1/2 in.

the column with 20 ml of cone.

in diameter.

R~mse

HC1 after introduction

of

the sample. Step 6.

Reduce the combined evaporation

effluents

on a hot plate.

to make the resulting

from the column to iO ml by

Add 20 ml of distilled

solution

about 2 M in HC1.

this solution through a iO ml Dowex

water Pass

f. column smd rinse

the column with 20 ml of 2 M EW1. Step 7.

Combine

the effluents

to dryness.

0.45

Dissolve

from the column and evaporate the residue

M HCI and proceed

them

in 25 ml of O. i M H2C204

as from Step 4.7 in the Procedure.

(Note 5). NOTES i.

Violent

effervescence

is prevented

by the use of the water bath for

cooling

and the slow addition of the hydrofluorie

acid.

-

PROCEDURE

Residusl

2.

other

3.

Fe ‘3,

CO+2,

elements

Ca+2,

Th+4,

freely

through

+6

Cr

, U

l “(CONTINUED)

+4

, Pa

+5

are held in the column Pb+2,’

+4

,Po,

+3

Bi

(log D> 1); while

and AC+3 of the elements

Ra+2,

Al+3,

of interest

pass

and the other

alkaline earth elements are slag not absorbed. +3 is held on the column, but would start to elute Al

at about 12 to

4.

volumes

of i. i M HC1.

It is recommended of very

5.

that a dust mask be worn to prevent

toxic

BeO dust.

The chemical

procedure

much as the initial chemical

incomplete

separation of stoney

*rylUum.

as given

radioactivity

The initial

specimen

The alkali

Ni ‘2,

elements

i5 resin

(no adsorption).

and about th~

yieId

usually

sometimes

from

might

that at least

to get rid of all contamtiting introduction directions eliminating introduced

after

difficulties.

Source

an excess

could be carried

a given

appreciable

recycles

amounts

of

may be necessary.

and inert

impurities.

The

following

prove

of value

8tep could

of EDTA

out following

indicating

the in

be

to hold back Al,

Step i 7 after

Be with NE40H.

of beryllium

- W. D. EhmamI Acts

although

would probably

PROCEDURE

Separation

100 percent,

Such an extraction

step i 3, using

o’r the extraction precipitating

HI-6;

inas -

on recyclfig.

step using ace~lacetone,

k Section

these

contain

activities

of an extraction given

exceeds

three

satisfactory

decreases

bulk constituents,

meteorite,

It appears

is not completely

the inhalation

~

from

iron

and T.

P.

2

meteorite Kohman,

material Geochim

et Cosmochim.

340 (1958).

Procedure: step

i.

Wash

the sample,

distilled

water

and any lacquer

which may weigh

and acetone which

to remove

from

iOO to 150 g, with

terre

skid

dirt

may have been used to preserve

specimen.

32

the

PRocEDuRE,2

Place

Step 2.

the sample

200 ml portions

(CONTINUED)

in a 21.

beaker

of aqua regia.

and treat

After

reaction

pour off each port ion into a separate treatment

S!!?EQ

until the specimen

To the combined

solutions

oxidation

(H).

of iron

with several

with consecutive. ha~ ceased

beaker.

Continue

is completely

dissolved.

add 25 ml of cone.

Evaporate

500 ml portions

HNO ~ to ensure

the solution

of cone.

this

to near

d&ness ., excess

HC1 to remove

HN03. Step 4.

To the smsll

volume

9 M HC1 to bring

a Whatrnan

A small

residue,

which to

300-400 Three

Filter

paper

graphite,

add sufficient the solution

in a Buchner

funneL

may be discaded.

and carriers

for

to separate.

other

radioelements

Transfer

tie

solution

separator

funnel and extract

iron with consecutive

ml portions

of isopropyl

saturated

extractions

the ether

50 ml portions Proceed

phase.

evaporation

up to i 1.

50 fUter

possibly

carrier

or four

Combtie

!&J&

No.

it may be desired

a 21.

the last

the volume

through

Add beryllium

from

beryllium

from

ether

are usually

layers

sufficient.

and wash them three

of 9 M HC1, as from

Add these

times

washings

Step 8 of Procedure

stone meteorite

with 9 M HC1.

material.

to the aqueous

1 for

(Notes

with

separating

1, 2).

NOTES 1.

The chemical cent.

However,

of beryllium

the weight

recycling;

imply�~g

ticomplete

separation

beryllium 2.

yield

See Note

present

$ometties

of BeO often

that the apparent from

S.

decreases

extra

bulk constituents

in the meteorite.

5 of Procedure

appears

yield

to exceed appreciably

cornea

rather

from

than from

iOO per on

Separation Source

of beryllium

- P. S. Goel,

Core i 39 grams

PROCEDURE

3

from de.ep-sea

sediments

D. P. Kharkar,

Peters,

and V. Yatirajam,

samples

of ocean-bottom

when dry.

carrier

N. Narsappaya,

Deep-sea

Research

sediments

Beryllium

addition of beryllium

D. Lal,

(I). B.

4_, 202 (1957).

weighed between 66 and

was recovered

by the following

from them without

procedure.

The recovery

eff icienty was determined to be 80 & i 0~0 by spiking some 7 sediments with Be tracer before the analysis.

sample

Procedure: Step i.

TO the dry sample HNO ~.

Heat to destroy

the acid. cone. Step 2.

add 500 ml cone.

Destroy

organic

nitrates

HC1 and 250 ml cone.

matter

by repeated

and to drive off evaporation

HC1.

Boil the semi-dry

residue

for i5-2CI min.

with cone.

dilute with 300 ml water and heat the mixture Allow the solids

Step 3.

of iron.

Combine

Boil the solid residue

the solutions

(Solution M).

of water.

Filter

of 6 N HC!l until (Solution L).

off any undissolved

Fuse the solid residue

weight of Na2C03

Wash

with i20 g NaOH in a glazed

dish for i 5 mi.n and filter

and dissolve

silica

solid

with five times

the melt in 100-i50

off and discard

HC1,

to boiling.

to settle and decant the solution.

the solid re~j~due with 100 ml portions free

with

any insoluble

its

ml

residue

(Solution N). Step 4.

Combine

solutions

Add ammonia Filter

Step 5.

Evaporate

M and N and heat to drive off (202.

to pH 8 to precipitate

the mixture,

precipitate

L,

discarding

in 200 ml cone.

silica.

Moisten

the silica

HF to remove

Si02.

hydroxides. Dissolve

twice with additions

Boil the precipitate

residue

of

with

(Solution O).

with H2S04

and heat with

Fume any remaining

ignite it and then fuse it with Na2C0s.

34

the

HC1.

400 ml of 6 N HC1 and filter Step 6.

the filtrate.

the solution to dryness

HC1 to precipitate

insoluble

residue

Dissolve

487.

with H2S04,

the melt

PRocEDuRE

in HC1 and filter.

Y!3z

Add ammonia

Combine

to Solution

precipitated

Step 8.

3 (CONT~UED)

hydroxides

the filtrate

O to bring and discard

the precipitate

in .500 ml 6 N HC1.

Extract

from

Fe(III)

of ether.

the solution

Concentrate

Filter

the filtrate.

Dissolve

by shak@

the aqueoue

Evaporate

Ti chlorides.

Add 8 g diso~um to 4. 5-5.0

phase

beryllium

Combine

from

shaking

by shaking Combine

of dilute

with four

solution

layers

Destroy

regia.

of Al and

to 50 ml volume. ahd adjust the pH

~40H.

Add 2.5 ml

with four for

i 00 ml portions

i O mhmtes

and back-ex@act

and evaporate

aIy, organic

Take

add

,,

each time. ,.

beryllium

475 ml portions, of 6 N HC1.

the HC1 extracts

dryness.

to i50 ml,

5 mtiutes.

the mixture

the benzene

with i liter

off the precipitate

to the solution

and shake. for

of benzene,

a~,a

EDTA

the

Add 300 ml of ether

the filtrate

by the addition

acetylace,tone Extract

F~ter

in HC1 gas.

O.

the pH to 8.

15 g NH4C1 and cool in an ice bath. and pass

with Solution

matter

up the residue

the solution

to

by evaporation

from

with

the evaporation

in

about 40 ml of i N HC1. Step i2.

Cool

we

solution

s olut ion.

Extract

the retire

CHC13,

and discard

aqueous

phase

by evaporation Step 13.

ti an ice bath

Decompose HC!l. residue

with three

40-ml

phase.

Evaporate

the

organic

ma~er

and decompose

portions

of

with HN03. nitrates

the solution

in 5 ml of dilute

at a time under

to dryness

residual

Evaporate

the organic’

and add iO ml of 67. cupferron

to a plastic

a heat lamp.

by boiling to dryness

HC1.�

counting

Transfer

the residue

with

and take up the the solution

dish and evaporate

a little

to dryness

Separation Source.

of beryllium

- P.

S. Goel,

Peters,

surface

4

from

sediments

deep-sea

D. P.

Kharkar,

D. Lal,

and V. Yatirajam,

A simplified bottom

PROCEDURE

procedure

sediments,

assuming

of the. clay

N.

Deep-sea

for recovering

(II).

Research 10

Be

from

that the @ryllium

pmicles.

Narsappaya; ~

B.

202 (i957).

samples

is adsorbed

of ocean-

on the

,

Procedure: Add

5 mg of BeO to the dried

500”C

in a muffle

furnace

tie

material

sample

for

and heat the sample

2 hours

to destroy

to

organic

matier. Step 2.

Leach

ignited

4 times

and then wash the insoluble until the washings Combine

the acid leach to small

in water

and add 400 g “of disodiurn

Add

volume.

solutio’n

the mixture

for

Step 6.

Tra&fer

Take

the

up the re”sidue

EDTA.

Adjust

the

- 5. and shake for

i O minutes

5 minutes.

Then

of benzene,

shaking

each time.

benzene

the washings

four portions

i)

and evaporate

with four portions

Wash the combined Disc=d

(Note

to 4.5

5 ml ace~lacetone the

with i: i HC1 solution”

and washing6

solution

extract

Step 5.

residue

HC1

are colorless.

PH. of the solution Step 4.

with i90 ml of cone.

extracts

with water

and back extract

at pH 5.

beryllium

with

of 6 N HC1.

the solution

dish and evaporate

‘a little

at a time

to dryness

under

to a plastic

a heat ‘l=p.

counting (Note

2)

NOTES, The procedure ace~lacetone

-benzene,

HC1 solution extraction

as quoted in the orig&l

after

extraction

the &sodium

with acetylacetone

of pH greater

than 4.5,

would be ne.ede d to bring

article

is carried EDTA

the st r~gly

38

that an

out directly

has been added.

must be carried

the considerable

stites

out from

qutitity acid solution

on the Since

the

solutions

of base which to the proper

PROCEDURE

pH would re suit in a very The

detdls

at giving given 2.

large

of the procedure

in the original

article.

specific

from

details

procedure

is capable

this point onward

3, 4 and 5 represent

an attempt upon information

material.

of beryllium

- J. R.

based

are not given

to what extent this stiplified io of recovering Be from samples of

PtiEDURE

Source

to be extracted.

article.

to be demonstrated

Separation

of solution

of the procedure

It remains

sedimentary

volume

Steps

in the original

4 (CONTINUED)

5

from

Clay

M.

Honda,

Merrill,

by a solvent

extraction

procedure.

and J. R. Arnold,

(to be published). Procedure: Divide

the clay

sample

of them. in a srnsll resistant

into ca.

amount

polyethylene

of water

beaker.

250 g of 48~, HF foIlowed

Trsnsfer slowly

the mixture over

viscous

a small

solution

Disperse

in a i liter,

heat-

To the mixture

slowly

by 80 ml of concentrated

Add about i O mg of berylUum Step 2.

100 g units.

carrier

add

H2S04.

to the mixture.

to a 300 ml platinum gas flame .“ Continue

which remains

each

begins

dish and heat very heat-

untfl the

to solidify.

Cool

the mixture. Heat the residue undissolved organic

with 300 ml of water.

material,

matter

bisulfate

treatment

solutions

from

present. solution

original

Add sufficient

Combine

add EDTA for water

3 liters.

37

mainly sulfates

is present

clay units (Note

amount estimated

to about

and calcium

is necessary.

solutions

consist

sample

the several

To the combtied over the

should

and aluminum

If much unattached

S.!zI+

which

CentrHuge

any of black (Note

further the supernatant

2).

in about 20% excess

completing to bring

4).

the Fe and Al

the volume

of the

PRocEDuRE

Adjust

Step 5.

the pH with ammonia

the solution and stfi a

becomes

separator

large

buffered

solution

with two i 50 ml portions

to cool,

Transfer

extract

with three

Combine of buffered

the pH to 6.4.

).

repeated’

additions

Boil

ammonia and ignite

countfig

to bring

with 200 ml

with two 50 ml

the HC1 extracts

nearly

of HNOs. ~ from

washing

h a large

HNO ~ and heat the Rolution

the solution

up the residue

funuel and

of benze”ne.

beryllium

add i O ml of cone.

and

until it is

to a Separator

back-extract Combine

EDTA

the solution

and stir

” and after

beaker, (caution!

the benzene

Allow

extracts,

of 6 N HC1.

Weigh

from

the

of 6 M HC1.

i 00 ml portions

water,

Discard

and add 45 g of disodium

portions

Take

beryllium

the solution

the benzene

4).

acetate.

then add i O ml of acetylacetone

dissolved.

-

to bring

(Note

complex

and wash them with “500 ml of

Back-extract

HC1 extracts

to

the beryllium

to pH 5-6 with dilute

enough ammonia

Step 9.

extracts

layer.

tie

When

the solution

of benzene

aqueous

Combine

Sten 8.

Transfer

funnel and e-act

the benzene

3).

again add 25 ml bf ace~lacetone

250 ml portions

Combine water

cool

to about 6.4 (Note

until it is dissolved.

witlrthree Step 6.

5 (CONTINTJED)

to dryness

with

..

the evaporation

the pH to” 8.

Filter

in water

and add

the precipitated

BS(OH)2

to BeO.

the BeO to determine (Note

chemical

yield

and mount for

5). ,, NOTES

i.

In

a

preliminary

a-model Wi~

2.

a Stockton

experiment,

and Be 7 tracer

shale

was used to measure

about 10 mg of beryllium

e*acts

of the sulfate

whereas

70 -80~0 of total

cake

carrier

contain

aluminum

Sometimes

the brown supernatant

(aluminum

compound).

”

sample

was used as

the recovery

of beryllium.

it was found that the hot water

almost was left solution

all of the, beryllium in solid

form.

contains

some

suspenfi ion

PRocEDuRE

3.

The color

of the iron

4.

Occasional

difficulties

layer 5.

The

- EDTA

5 (CONTINUED)

complex

of separation

is useful require

ag an indicator.

centrifuging

the organic

at this step. over -~

yield

been sufficient samples

of beryllium

to remove

which were

is about 60-70%.

all radioactive

analysed,

The procedure

impurities

but beryllium

from

carrier

has

the clay

is necessary

for good results.

PROCEDURE Separation Source

of beryllium

- J, R. MerrUl,

from

clay

M.

Honda,

6

by ~

ion exchange

procedure.

and J. R. Arnold,

(to be published).

Procedure: Steps

i-3

As k Procedure 200-300

Step 4.

T&e

5, using

g clay

O. 5 ml of the combtied

Fe and Al (Note Add grdudly 5 CaC03 over

(Note Add

complexiometric

of the sulfate titration

of 2 H4Y + i Na2H2Y*

mMxre

to the solution

until about O. i mole

to complex

60 ml of glacial

Fe and Al,

with more

acetic

off the insoluble and washings the solution

exchange

column

has passed

for

2 H20 of excess

MS ken

CaC03

+ EDTA,

added.

(usually

about iOO g).

adsorbed

a i ~ter

NaAc

and 1 M HAc. contdn

form.

3). the

solution

of O. Oi M EDTA

any traces

with a solution

0. 5-4.5

all the beryllium. 39

this

column

+

of Al and Mn

“4).

the column About

50 x 8 ion

Mter

1 liter

remove

to

on the COILUIUI. (No* from

Dowex

pass”through

+ O. 5 “M HAc

beryllium

(Note

- CaCO ~ and dflute

CaS04

in the Sodium

Elute

effluent

acid as a buffer

to iO liters.

through

though,

O. i M NaAc

W,?&

extracts

2).

filtrate Pass

a

the pH to 3.5-4

Filter

Step 7.

by EDTA

aqueous

i).

that needed

Adjust

for a

sample.

cake and analyse

Ste.u 5.

20 mg of BeO carrier

of O. 5 M

volumes

of

PROCED~E

EsE&

Precipitate

Be(OH)Z

ammonia.

Filter

to determine

6 (CONTINUED)

from

the effluent

the precipitate

chemical

yield

by the addition

and ignite

of

to. B@.

Weigh

and mount for counting.

NOTES

i.

For

discussions

halyst

of complexometric

80, 713 (4955);

Schwsrzenbach, Titrations”,

2.

W@tgart

G. Schwarzenbach Inter science

Calcium

carbonate

concentration

If appreciable

&ounts

step.

the ion exchmge

In the presence

the solution,

the most

this enough HAc

Methuen

Beryllium

in solution

resin

of excess

EDTA

important

variable

is added to the mixture

and Co.

Ltd. ,

( i95 7).

the pH so that we

of Mg or Ca are

G.

“Complexometric

Irving,

not be increased.

with CaS04.

Titration”,

Inc. , New York.

is used to raise w~

Na+ from

( i955);

and H.

Publishers,

copercipitated

replace

see G. Schwarzenbach,

“die Komplexometrische

Enke,

London,

lyte

3.

F.

titration

electrois not

they will

used in the succeeding this increases

the pH of

in the process. to make the final

To prevent solution

O.”i M. 4.

The completeness titration

of removal

caq be checked

of the effluent.

PROCEDURE Separation Source

by complexometric

of beryllium

- J. R. Arnold,

from

7

clay

Science

~

584 (i956).

Procedure:

EkP2”

The sample, clay,

consisting

is. treated

of several

with a mixture

500 g of i2 N HC1 in two i liter 10 ml of BS carrier has been added.

‘ 40

grams

of wet

of 500 g of 48% HF and HH polythene

(approximately

Evaporate

hundred

beakers,

after

60 mg BeO equivalent)

to dryness

in a hot-air

jet.

PROCEDURE

Add i50 gofeach Evaporate

acid and again

to dryness

of HC1 to remove Take

twice

most

up the sample

centrifuge.

7 (cONT~UED)

more

After which

solid

boil,

dec,snt,

with H2S04

and

until

pH 6 to 6.5.

and fuse sny rematig

dissolving

remtis

the melt

and combine

650 g of tetrasodium

solution

of 500 g

cease.

with -4.

Add

with a total

in i500 ml of i N HC1,

Talce up the cake with water

any solid

to dryness.

of the� fluoride.

Heat the remaintig

HF bubbles

evaporate

EDTA

in water,

for

and bring

5 minutes

portions

of reagent-grade

extracts

and backwash

discard

sdl solutions. the solution

Add 25 ml ‘of acetylacetone,

has stood

solid

and sfter

extract

benzene.

the

with three

Combine

them with acetate

to

250-ml

the benzene

-buffered

water

at

pH 5.5 to 6. Ex&act

the benzene

HC1 and discard EDTA

layer

with two i 50 ml portions

the organic

to the aqueous

phase.

extracts

Add iO ml of acetylacetone, stood Sten

7.

extract

Combine

the benzene

buffered

water

two 50-ml Boil

portions

Weigh

the pH to 6 to 6.5.

the solution

75 ml portions

extracts,

backwash

of 6 N HC1.

down the aqueous

phase

organic

and precipitate

precipitate

and adjust

hks

of benzene. them with acetate

at pH 5.5 to 6, and then back-extract

of HNO ~ to destroy water

Add 45 g of disodium

and after

it with three

of 6 N

and ignite

Discard

nearly matter.

Be(OH)Z

the organic

to dryne as wi& Take

up h

with ammonia.

with phase. the addition

50 ml of Filter

the

to BeO.

the BeQ to determine

for counting.

41

chemical

recovery

-

and mount

P~CEDURE Separation Source

of beryllium

- E.

Baker,

i3i9

from

8

aluminum

G. Friedlsnder,

tsmget material.

and J. Hudis,

Phys,

Rev.

ix

(1958).

Bombarded

aluminum

quanta that interfere

witi

targets

contain

the counting

22

Na

, which

gives

of the 0.48 Mev

O. 54 Mev

y ray of Be.

Procedure: Dissolve

the aluminum

Precipitate Centrfige

!2EE!-z

Dissolve acid,

beryllium

and aluminum

and discard

the aqueous

the mixed

Centr~ge

and discard

Evaporate

the liquid water

Centrifuge Dissolve

Step 6.

Take

the solution ba~.

acetic,

acid three

an equal volume. Evaporate residue

tie

by adding

YsIw

Fflter” filter

a powder, weighed determine

slurry ftiter

acetic

acid

times. of crystals

of basic

beryllium

the CHC13” solution

to ne~

three

the aqueous dryness.

with water.

Aga+

to a

times

with

layer.

Take

up the

take the solution

Precipitate

Be(OH)Z

of HN40H.

precipitate

through

to a platinum

at 1000° for

i hour.

with 5 ml of ethanol

paper

chemicsl

in glacisl

Discsrd

dilute

Transfer

and ignite

phase.

with

more

excess

bath.

Be(OH) ~ with ammonia.

amount of HNO ~.

the Be(OH)2

paper,

on a stem”

to dryness

CHC13 layer

and them

paper.

volume

6 H20.

the evaporation

of water.

a slight

of AlC13.

Wash the. CHC13 layer

h a small

to dryness

with HC1 gas.

to dryness

consisting

funnel.

in

Evaporate

@ CHC13 and transfer

sepsratory

cool

to a casserole.

Repeat

up the ,solid,

acetate,

EkEz

and precipitate

of Be(OH)z

on a stemn glacial

phase to small

the precipitate

hydrochloric

to the solution,

the, precipitate

the aqueous

agd transfer

with ammonia:

phase.

the solution

and discsrd

carrier.

hydroxides

in concentrated

of ether

and saturate

Add distilled

Step 5.

hytioxides

add am equal volume

an ice bath,

EEF+

in acid and add beryllium

disc.

Dry

yield.

a ~atman

42

crucible,

char the

Grind

the BeO to

and filter

onto a

in an oven and weigh

Mount for counting.

42

No.

to

PROCEDURE Separation Source

of berylllum

- J. D.

Essentially Friedlander, separation Two

cycles

from

Buchanan,

mixed

fission

J. Inorg.

the sane

Nut,

procedure

and Hudis,

Phys.

of beryllium

from

of 3 x 408 and a chemical

products

Chem.

~

Rev.

43i9

i40 (i958). by Baker,

(i958)

targets

have resulted

yield

~

and uranium.

has been described

cyclotron

of the procedure

9

for the

of copper,

silver

and gold.

in a decontamination

factor

of 9070.

Procedure: Dissolve

the ssmple

beryllium

(about

centrfige

tube (50 ml).

with a slight

Dissolve through

cone.

of NH40H.

the Be(OH)2

HC1.

Be(OH)z

precipitate

the Be(OH)2

coagulates.

solution

to a clean

supernatant

of NH40H.

solution.

h mti.

with 5 ml tube.

Wash

Cen-

the

the wash. of cone.

with sttirtig,

HC1.

Add

and heat until

and decant the supernatant

tube.

with HC1 and then precipitate of NH40H.

Centrifuge

Be(OH) ~

snd discard

the

solution.

the precipitate

the solution solution

using

indicator

k

3 ml glacial

to i5 ml with water.

acetic Add

acid and 2 ml of i O?fO

and then adjust the pH to 5 with ~40H paper.

Add 2 ml of acetyl.acetone a minute

excess

Pass

to 15 ml and heat on a water

centrifuge

excess

EDTA

for

the

which has been

and discard

Centrifuge

the solution

with a slight

dilute

dilute

O re&

HC1.

h a centrMuge

precipitate

i O ml 8 N NaOH

Fe(OH)s

Dissolve

Be(OH)z

and discard

Wash the resin

the supernatant

3 mg Fe HI carrier,

Acidify

in a

iO ml cone.

iX-i

with a slight

with i 5 ml of water

Add

h

i).

the effluent

and discard

bath.

Centrifuge

of Dowex

HC1 (Note

Collect

Reprecipi&te

Dissolve

contied

then precipitate

precipitate

column

with cone.

trifuge

Stti well,

and add

solution.

a short

washed

acid

i 5 mg) to “the sample

excess

supernatant Step 2.

in an appropriate

and stir

with a mechanical

43

the solution

sttirer.

Add

vigorously 7 ml of benzene

Procedure

and extract

9 (CONTIPTUED)

beryllium

with the mechanical arate

&rQ!2

sttirer.

and transfer

of a transfer

of the aqueous

phase

Repeat

step

7 twice

Back extract benzene Allow

berylMum

solution

Step 42.

and transfer

ustig

a transfer

combining Discard

go

for

i min.

the HC1 solution

pipette.

the HC1 extract the benzene

just to dryness

3 and evaporate

with the first

layer. (do not bake).

just to dryness.

2).

Dissolve

the residue

Transfer

step ii

with suction

on Whatman

and precipitate

of ~40H

inside

the BeO to a tared

filter

Wash with ethanol

and dry at 90-100°

the sample scopic.

as quickly

by slurrying

as possible

Mount 13s0 for

and dry under

inhaling

with a stirring paper

42 paper.

to BeO

is snow white.

a hood to avoid

the BeO to a powder

No.

the precipitate

i hr or until precipitate

With the crucible

HNO 3 and

to precipitate

to a crucible

Ignite

or in a iOOO oven.

at i 000 ‘C for

in 2 ml of cone.

excess

the paper

a heat lamp

from

Add a slight

Filter

Be(OH)z.

grind

extracts

i O ml of 6 N HC1 to the

to separate

the HC1 solution

iO ml of water.

Step i 3.

the pH

the benzene

vigorously

Add 5 ml of cone. (Note

combining

and stirrtig

step 9 once,

Evaporate

Check

centrifuge

to pH 5 H necessary.

by adding

in the 150 ml beaker. Step ii.

to a clean

to sep -

step 7.

the phases

Repeat

phase

and readjust

for a minute

the two phases

pipette.

more,

to a 450 ml beaker Step 10.

vigorously

AUow

the benzene

tube by means

with that from

StsE221

by stirring

for

rod.

BeO dust, Transfer

with alcohol. iO min.

Weigh

as BeO is somewhat

hygro -

counting.

NOTES i.

The ion exchange dismeter

column

to the bottom

tip with glass

wool,

is made by sealing

of a i 5 x 85 mm pyrex

and filling

a tip 5 mm long by 2“mm test tube,

the tube with resin

of about 1 inch. 44

plugging

to a height

the

PROCEDURE

2.

E a higher residue

of beryllium

- J. B.

Ball,

G. Mitra

sandwiched

targets A.

W.

the

from

etep 2.

Fairhall,

the tuget

and bombsrded

from

under

the target

and

these

conditions

in the silver

that a large

is

with up to 44 Mev helium

ti the silver

fofl

several

foil

of target

The

over -all

and silver

catcher

fofl.

itself.

hold-back

of the beryllium.

number

much modification.

meterial

is caught in the silver

the decontamhation

general

without

Jr.,

is used where

of impurities

is sufficiently

Bouchard,

foils

escapes

are used to improve

ti excess

from

silver

No Be7 is produced

handled

i o

cyclotron

dissolve

the procedure

P-EDUm

G. H.

between

of activation

H(21 and repeat

procedure

Be 7 which

is needed,

(unpublished).

The followtig

ions.

of decontamtition

in 10 ml cone.

Separation Source

degree

9 (CONTINUED)

Because

carriers The procedure

elements

chemicsl

could be field

is

of 80~0.

Procedure: Dissolve

the target

Evaporate

most

(iO mg).

Add hold-back

Hg and Tl, Dflute

of the excess

where

the mixture

the mtiure centrb%ge

Add cone.

NH40H

the Be(OH)z

tube.

precipitate

which

i).

well

the mixed

the precipitate. Centrifuge

4s

h

coagulated. solution

the precipitate.

Dilute

is

precipitate

the aqyeous

mnount (about

may be present.

and pass

until the solution

and discard

about 20 ml with water.

HNO ~.

In, Au,

the supernatant

Discard

in sufficient

from

(Note

ae

snd decant

Centrifuge

and sulfides

Add 6 N NaOH

sulfides

to ‘We solution

ammoniacal.

Be(OH)z

ZnJ Cd,

to about 20 ml with water

to a clean

faintly

of Cu,

as nitrates

H2S until the precipitated Centrifuge

in cone.

acid snd add Be carrier

carriers

possible

foils

of

phase.

i ml) to dissolve the mixture

and discard

any

to

PROCEDURE

To the supernatant Fe JII carrier, precipitated

10 (CONTINUED)

solution add 3 to 4 drops of i O mg /ml

with swirling.

Fe(OH)

Then

Centrifuge

Dissolve

the BS(OH)2

HC1.

Dilute

discard

the supernatant

HC1.

beryllium

the Be(OH)2

Dfiute

iO minutes

Before

Step 9.

of EDTA

centrifuge

precipitate

of a saturated

for

BaBeF4

of precipitation

of Ba solution

and cone.

water

and filter

millipore and @

filter

more. of cone.

cone.

bath and addition

Continue

of 5 ml heatjng

the precipitate. solution

check

for

i drop more

each

HF.

the suspension (Note

2).

amount

through

of distilled

a weighed

Wash with distilled

Weigh

as BaBeF4.

RA -type

water

Mount for

counting.

NOTES i.

Gold carrier AgC1.

A small

no difference 2.

The precipitate filter

necessarily

through

amount

contains of AgCl

to the recovery is very ordinary

chloride

precipitate

ion which precipitates in the mixture

makes

of beryllium.

fine -grained filter

and

the solution

water

by adding

up in a small

in an oven.

transfer

of Ba(NO q) ~.

the supernatant

the precipitate

Centrifuge

the precipitation

twice

by dropwise

and then centrifuge

discarding

salt of

in a minimum

in a boiling

solution

and

tube and add 30 drops

completeness

Take

Repeat

precipitate

Heat the solution

slowly

with NH40H.

to 20 ml with water,

to a 50 ml plastic HF.

of the disodium

solution.

in the presence

amount of

to 20 ml with water

solution

Precipitate

to turn the “indicator

in a small

the solution

acidify

of Be(OH)2.

precipitate

EDTA.

Dissolve

the

and barely

NH40H

the precipitate

add 2 ml of a safirated

of Be(OH)2

red indicator

add sufficient

yellow.

cone.

and discard

q.

Add a drop or two of methyl the solution.

Centrifuge

paper.

46

and next to impossible

to

11

PROCEDURE Radiochemical Source

- T.

separation T.

Shun,

of beryllium

in “Collected

Los .Mamos

Scientific 1.

The determination

Laboratory

decontamination

step carried

hydroxide

precipitation

solution.

Berylliwm~

Stepsy of basic beryllium

ammonia

water.

precipitations cam-iersp

The hyd~oxide

in the presence

by acetic

into cb.loroformp dissolved

oxidep 13e0,

yields

Beryllium

have not been determined, emitting

impurities

it appears

antimony,

and tellurium

is then changed to the

is finally

i8 hours and gives

that decontamination

io mg MO /ml (added as NH.4)61M07Q24 0 4H20

Sb carrier:

.10 mg Sb/ml

(added as SbC15 in 21JIHC!I)

Te carrier:

40 mg Te /ml

(added as TeC14 in dilute HCI)

c onc.

HNO ~:

cone.

factors

from

gamma-

as c.p.

in H20) (added as F’eC13 . 6H20

47

as

chemical

Reagents (3. 00 mg BeO/ml}--(addecl

is

to the

The procedure

IWOcarrier:

Hcl:

acetate

converted

10 mg Fe/ml

6 M —

is e%~racted

and the bzsic

Fe carrier;

Hcl:

with

is of a very high order.

- 4H20

in

of acid sulfide

of 35’70, .kltlmugh decontamination

i. 082 rng Be/ml BeS04

remains

precipitated

it is weighed and counted.

2. Be carrier:

is a ferric

nature$

by a series

is evaporated,

approximately

in the neighborhood

The first

The ‘basic acetate

Beryllium

acetate ~

T%e beryllateis then

hydroxide

hydroxide

acid treatment.

in which form

2“

of molybd.enum$

acid solution.

outlined below requires

or Na2Eie0

is purified

the chloroform

in nitric

(4958)

of sodium hydroxide

of its amphoteric

ion and beryllium

respectively.

basic acetate

by chlorofcmm.

by mesms of an excess as a result

to beryllium

2nd ed.

out on a solution of the sample

solution as a berylla’ce ~ NaH13e02 converted

Repo??t La-1721,

(Be 7, is based upon the fcwrnationj

(OCCWH 3)6, which is extractable

decontamination

Procedures”,

Introduction

of radioberyllium

after the appropriate Be40

.Raciiochemical

in dilute HCI) in H20)

PRocEDuRE

HC2H302:

11 (CONTINIJED)

glacial

NH40H:

cone. 20~0 by weight

NaOH:

aqueous

solution

gas

HZS :

Chloroform:

anhydrOuS

Ethanol:

absolute.

Equipment

3.

Fisher

burner

Drying

oven

Muffle

furnace

Centrifuge Block

for holding

Mounttig

cent@fuge

tubes

plates

Forceps Tongs

for Erlenmeyer

flasks

i O-ml beakers

(one per

sample)

50-ml

(two per

sample)

beakers

Pipets:

i-

and 10-ml

i25 -ml

separator

funnels

i 25 -ml Erlenmeyer Ground-off

Hirsch

Filter

chimneys

Filter

flasks

No.

No.

(one per

funnele: (one per

Coors

sample) 000A (one per

sample)

ffiter

circles:

7/8� diameter--washed

with ethanol,

and weighed

42 Whatman

filter

paper

2“ 9 600 ffiter

funnels

40-ml

centrifuge

conical

Wash

boffle

Stesm

bath

(four

(9 cm)

per sample)

tubes:

Pyrex

8320 ( i4 per sample)

Hot plate Stirring

sample)

(one per sample)

42 Whatman dried,

flasks

(two per sample)

rods.

48

PROCEDURE

4. Dissolve

Preparation

of Standard Beryllium

iO. 62 gm of c. p. BeW4

which has been dried overnight solution containing

Pipet

exactly

conical

addition

5 rein,

Transfer

during

the transfer.

O. 5 ml of Fe carrier

clean

stirring.

Heat

centrifuge

tube,

on a steam

Stir

bath for

to a clean

centrifuge

for Step 4.

to the supernate transfer

and retain

20~0 NaOH

concentration.

q precipitate

Centrifuge,

to another

sufficient

the supernate

the Fe(OH)

and

by the dropwise

the solution

a 5~0 NaOH

transfer

and retain

of the sample

to neutral

contains

solution

centrifuge,

vigorous

into a 40-ml

snd add O. 5 ml of Fe

nearly

tube which

the comb~ed

vigorously

Add

Heat to boiling

the solution

centrifuge

to give

a

mg BsO /ml).

Be carrier

tube and add an aliquot

of 20% NaOH.

40-ml

to 3.00

This gives

Procedure

HC1.

Bring

Co. ),

h 500 ml of H20.

at i05°,

centrifuge

carrier.

Step 2.

(Brush Beryllium

iO ml of standsrd

i ml of cone.

tube,

c 4H20

Carrier

i. 0132 mg Be /ml (equivalent

5.

E!SE!&

11 (CONT~UED)

with constant, the supermate

the Fe(OH)

to a

~ precipitate

for

Step 4. -

Neutralize Make

the supernate

the solution

ammoniacal

5 min on a steam least steD 4.

10 rein,

Combine

proceeding

the combined

207. NaOH

NaOH

tube,

supernate cone.

into another solution

to give

and transfer

Steps

Heat

the supernate

HC1.

(Note

at

Dissolve Transfer

sufficient

solution

bath for

a 5q0

5 min.

to a ‘clean centrfige i).

HC1 and then make

49

i and 2.

tube conttiing

on a steam

Heat on a steam

Heat for

stand for

of cone.

to the combined

the precipitate

with cone.

NH40H.

centrifuge

HC1.

with Step 4.

from

h a minimum

of cone.

NH40H.

in the meantime

precipitate

d.iscsrding

with cone.

q precipitates

concentration.

Centrifuge

addition

bath and then let the mixture

the Fe(OH)

the solution

by the dropwise

bath for

Neutralize it ammoniacal i O mti.

the with

PRocEDuRE

EEP_a

Centrifuge

the Be(OH)2 precipitates

Combine

both supernates Combine

(Note 2). the larger.

&!34

11 (C0NTIT4UED)

formed

in Steps 3 and 4.

in a i 25 -ml Erlenmeyer

both precipitates

flask

by washing the smaller

Stir to break up the precipitate

into

and then centrifuge.

Transfer

the wash liquor to the i 25 -ml flask above.

Dissolve

the BS(OH)2 precipitate

in a slight excess

of cone.

HC1 and repeat Steps i -5. Step 7.

Dissolve

the Be(OH) ~ precipitate

add an additions with H20. 5 mti.

Add

tube,

Heat the aupernate

into a clean

carrier. through

evaporate stirring

to expel

centrifuge

over

and evaporate

over

Let

time

before

funnel.

decanting

Retain

HC2H302

with Acidi&

and

with constant

being

to room

HC2H302 careful

not to

point of basic temperature

with CHC1s,

using

of CHC13 and centrifuging

material

60

ammoniacal

3300, the boiling

the supernate

the solid

60” funnel

the supernate.

a flame,

acetate

5-ml portions

i 0- and three

using a 2“,

5 ml of glacial

the tube cool

beryllium

and filter

3).

to dryness, Add

beryllium

the basic

paper

5 ml of glacial

nearly

exceed

extract

centrifuge,

and discard

let the temperature acetate.

the precipitate.

H2S and then make

to dryness

the supernate

H2S and add O. 5 ml of Te (IV)

filter

a low flame.

the supernate

the precipitate.

discarding

witi

the solution

and

O. 5 ml of Sb carrier

with H2S,

Centrifuge precipitate

2 to 3 rein,

and decant

tube (Note

to expel

NH40H.

the Be(OH)Z

tube,

Heat the supernate

transfer

Add

CentrHuge

42 Whatman

Heat the filtrate cone.

H2S.

and saturate

a No.

into another Step 10,

to expel

centrffige

Boil

Centrifuge,

in H2S for

into a clean

in H2S for

tube and discard

with H2S.

Heat the supernate

and bubble

the supernate

pass

of 6 M — HC1,

and dilute to i O ml

the precipitate.

bath,

centrfige

and saturate

WI@

discarding

to 20 ml with H20.

to the clean Step 8.

and decant

10 min on a steam

dilute

of 6 — M FfCl,

O. 5 ml of Mo carrier

Centrifuge

centrifuge for

milliliter

in a minimum

into a i25 -ml in the centrifuge

one each

separator tube.

and

PRocEDuRE

II (CONTINUED)

Wash the CHC13 extract HZO,

transferrhg

containing

the materisl

paper

tito

a clean,

CHC13 is being

from

through

dry 50-ml

Evaporate

evaporated,

of cone.

Step 12.

Dissolve by heathg

to proceed =

the solution

by the addition supernate.

iO -ml beaker. to dryness.

Ignite

slurry

it to the basic

acetate

adding the

in Step i O. CHC1 ~ extract

If it ie felt that proceed

it is necessary

NH40H.

Steps

ordinarily

for

No.

circle

suction.

the funnel and weigh.

for

tube,

and precipitate

Centrifuge

to i to 2 ml and tiansfer

continue

heating

3 to 5 ml

42 Whatman funnel

ethanol.

the

filter

requires

circle

set up which

Permit

the solid

ethauol,

and

in a filter contatis evenly

about iO rein) before

Mount and gamma -count

51

furnace.

to settle

by pulling

then dry at 405° for

Be7 has only a 476-kev

to a

(on a hot plate)

of absolute

Dry the precipitate

2 to 5 rein;

Be(OH)2

and discard

i hour at 250” in a muffle

(this

Dilute

7-i 2.

-ground -off Hirsch

on the fflter

centrifuge

to i5 ml with H20

the EeO with

i O ml of absolute

4).

by

If an appreciable

HN03.

However,

Carefully

pour onto a tared

(Note

the

material

the evaporated

of cone.

the HNO ~ solution

applying

convert

to a clean

of cone.

Repeat

Evaporate

chimney

While

as in Step i 3.

Transfer

Cool,

600 filter

Be(OH)2

has been obtained,

to Step 44.

the HNO ~ solution

s

bath.

Centrifuge.

from

decontamination

immediately

a 2“,

filter

with Step ii.

to that obtained

with a mtiimum

sufficient

using

the CHC13 extraction;

acetate

tube

42 Whatman

Precipitate

is formed,

extracted

the basic

proceed

NH40H.

of Be(OH)2

acetate

No.

beaker,

HC1.

as in Step iO and repeat basic

~

of

by CHC1 ~.

and the CHC1 ~-insoluble

Step iO with cone.

quantity

to the centrifuge

the CHC1 ~ on a steam

the wash liquor

the addition

portions

which was not extracted

the CHC1 ~ solution

Acidify

with 4-ml

the wash liquor

Filter

funnel.

Step 11.

four times

air through i5 min.

in scintillation

gamma

ray.

Cool

cou@er

PROCEDURE

11 (CONTINUED)

NOTES 1.

#m additional increases

2.

recovery

of Be from

the chemical

The

supernates

are

saved

from

yield

3.

as a precautionary

volume quanti~

Steps

8 and 9 probably

three

carriers,

Counting period

Mo,

these

formed

A

with Step 7, i. e. , all

could be added at the same

of at’ least

and is cent.hued

53 days (one half-life

any impurity

which’ is both a beta and a gamma

of beta activity

time

and

amount

enough to impart

a yellow

to the basic

acetate

6— M HC1 before

The solids

from

About

to i20°;

be exercised

color

to determtie emitter

is contaminating

precipitate,

to make

acid evaporation

just prior

an ether

are heated

the formation

30’7%of the Be is converted

e*action

to a temperature

of basic

to the basic

95 to 97% is converted

at 220° C.

to prevent

“the temperature

excee~

the basic

acetate

in a constant

from

already

formed.

temperature

beryllium

acetate

however,

is best accomplished

i. e.,

proceeding.

220” C to complete

thus decomposing

whether

with the beryllium,

to the Be(0H)2

it is advisable

the acetic

of approximately

to check

Procedure

of iron remains

step,

It is well

for a

for.

to Beryllium

E an appreciable

at intervals

of Be 7,.

for the presence

ii8

of Be.

as sulfides.

is begun immediately

acetate.

recovery

to

by this treatment.

immediately

from

3 and 4

can be evaporated

further

could be combined

Addendum

2.

supernates

is ‘always

the Be7 and must be corrected

i.

in Steps

If much Be(OH) z appears

for

Sb, and Te,

~ Step 4

i to 27”.

ammoniacal

of Be(OH)2

~ precipitated

precipitations

measure.

stage,

and made

small

precipitated 4.

by about only

the BS(OH)2

to have been lost at this a small

the Fe(OH)

at

Care

must

330° and The ftial

heat%

oil bath or under

a

heat lamp. 3.

The final;’ ‘aluminum filtered.

-0,

aftdr

counting

i&uition

plate

at 500° is transferred

rather

More” reproducible

than being

results

52

are

slurried obtdned

dtiectiy

to an

with alcohol in this manner.

and

PROCEDURE Separation Source

of Beryllium

- G. M.

from

Iddings,

Fission

i2

Product

In “Radiochemical

Mixtures

Procedures

in Use at the

University

of California

Radiation

Laboratory

(Live rmore)”,

University

of California

Radiation

Laboratory

Report

UCRL

-4377

(1954). From

Purification:

a 4-day

old solution

about 109 beta counts obtained About

Yield:

SePar ation time:

which

per mbmte,

ehowed

a beti

About

six hours

activity

solution

exclusive

of mixed

of Be 7 was

of about 7 c /m.

the solution

precipitate

of ignition.

activities,

and about 5 mg of lanthanum Mske

a sample

~d

70 per cent

To an acid

=

44 fissions iO

containing

carrier.

mnmoniacal.

with Mute

add i O mg Be carrier

ammonia.

Centrifuge

and wash

Discard

supernatant

and

wash. Step 3.

Add i O ml 3 ~ than five leach

NaOH

minutes

to the precipitate.

in a not water

with another

Digest

bath.

10 ml 3 N NaOH.

for not more

Centrifuge. Combine

Repeat

NaOH

supernatants. Step 4.

Add

-5

Discsrd residual La(OH)s. +4 carrier to the NaOH solution. mg Te

of a saturated solution

solution

of NH4C1.

ixvice with water. Sten 5.

Dissolve -

Discard

5 drops

i5 ml of a saturated

and wash BS(OH”)2 precipitate

supernatants.

Be(OH) z in 3 or 4 drops solution

of cone.

HCl~

of O. 5 N Na2S03

and add

and i N — NaHS03

6).

“Transfer

solution

separator stopcock) Add

Add -

CentrHuge

15 ml of a buffer

(-pH

of Na2S.

Add

funnel

to a 60-ml, (with

stem

cylindrical, detached

open-top,

immediately

below

the

.

30 ml of O. 40 ~

and equilibrate

phases

a motor-driven

glass

TTA

(thenoyltrifluoracetone)

for ten mhmtes rod stirrer

53

by rapid

(paddle).

in benzene stirring

with

PRocEDuRE

WE!&

Step 9.

Wash

organic

phase

three

minutes

for

twice

phase

minutes

each wash (see

twice

phase

composition

is N ii

with -

Step iO.

H2S04)

formic

acid and i part

Make

consisting

cone.

Repeat

solution

allowing

(ii

whose

ml cone.

ten minutes

for

2).

i 5 ml of a solution

i5 minutes.

for five

with z i2 ml of a solution

N HC1 and 1 M — H2S04 —

Add -

for

Wash

i).

six times

Note

mowing

the sulfite).

i 5 ml of 8 — N HN03

Note

HC1 with O. 7 ml cone. each wash (see

with N i 5 ml of water

each wash (to remove

organic

Wash organic

12 (CONTINT.JED)

of two parts

HC1.

Agitate

and combine

ammoniacal.

layers

aqueous

Centrifuge

cone. together

layers.

the precipitate

and

wash with water. Add

10 ml of 3 ~

NaOH

and add Br2 dropwise

Stir.

Add a saturated

becomes

yellow.

dropwise

until solution

excess

becomes

solution

colorless,

(to keep any Te in solution

until solution of Na2S

then add 5 drops

when the pH is lowered

to 9 or 10 in the next step). Add

10 ml of a saturated

precipitate

solution

of ~4C1.

Centrifuge

and wash with water.

Acidify

with HC1 to pH 3-4 (by adding -20 ml of O. i ~ HC1). +++ carrier. Warm to - 60”c in water bath. Add .W 5 mg Fe ml of 5~0 8-quinolinol

Add i.5

2 — N NH4AC

minutes Fflter

Make

through

Whatman Step i7.

Ignite

Step 18.

Transfer

No.

42 Whatmsn

basic

paper.

to w pH 5.

then cool to room

of Be from

filtrate

Al,

Pa,

paper. Zr,

with NH40H.

Wash with

iyo

Add 5-40

Let

stand for five

temperature. Discard

precipitate.

Nb and others.

Filter solution

ml of

through

)

No.

42

of NH4Ac.

to BeO for one hour at iOOO “C. to tared

is somewhat (diluted

solution

in 60 “C bath,

(Separation Step i6.

to br~

in 2 — N HAc.

aluminum

bygroscopic.

fourfold

hat and weigh

rapidly

) Add a few drops

with ethyl

54

acetate).

(BeO

of Zapon

PRocEDuRE

12 (CONTINUED)

NOTES

i.

Te

+4 . m slowly

along

reduced

at the titerface

of the benzene-aqueous

wash with 8 N — HNO 3 will placing

2.

iO or 12 ~ HC1 will phase.

If very steps

large

finely

retire.

divided

The paddle

A 5-minute +4 Te metal to Te ,

stirrer

bring

very rapidly. +4 from O. 4 M Np

is necessary

to

together

i2 N — HC1 with some

to be extracted 3.

oxidize

it h the acid layer.

churn the two phases

and it is carried

to Te metal by the sulfite,

sulfate

into the aqueous amounts

cause

Zr,

tito

the aqueous

and some

of Pa,

phase.

of protactinium

must be added to remove

will

TTA

are present

this activity.

55

initially,

extra

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