v
National
Research Council
m
NUCLEAR SCIENCE SERIES
The ~Radiochemistry
of Aluminum
I
.,:
1
————.. —..,
“s,
and
Gallium
COMMITTEE
ON NUCLEAR
L. F. CUR~,
Chairman
Nsfional
Bureauofstandards
SCIENCE
ROBLEY D. EVANS, ViceChatrman
Maemiclmaerta
Lgstinw.e
ofTechnology
J.A. DeJUREN, .%mretary
Weatinghou,ge
Electric
corporation
C. J.BORKOWSKI
O=k RidgeNaticmai
Laborawry
J.W-.IRV~E, JR.
MaaeachueettaInstitute
ofTecimol~
ROBERT G. COCHIMN
Texas A@cultural and Mechanical
College
E. D. KLEMA
Nordmestmm Unfverst~
W. WAYNE MEINKE
University
ofMichigan
SAMUEL EP8TELN
California
Institute
ofTechnology
U. FANO
National
BWSSU
J.J.NICKSON
Memorial Hospital,
New York
ofStandards
ROBERT L. PLATZMAN
Laboratoire
de ChimiePhysique
HERBERT GOLDSTEIN
NuclearDevelopmentCorpx%mionof
America
D. M. VAN PATTER
Bamcd ResearohFoundation
LIAISON
MEMBERS
PAUL C. AEBERSOLD
Atomio EnergyCommission
CHARLES K. REED
U. S.~r Force
J.HOWA.RDMOMILLEN
National
ScieneeFoumM~ion
~~~~
E. WRIGHT
OfficeofNavalReseamh
SUBCOMMITTEE
ON
RADIOCHEMISTRY
W. WAYNE MEJNKE, Ch.ui~
University
of Michigan
HAROLD KIRBY
Mound Laborato~
GREGORY R. CHOPPIN
FloridaStem Universly
GEORGE LEDDICOTTE
Oak RidgeNationai
Laboratory
GEORGE A. COWAN
Loa Alamoa Scientific
Laboratory
JULIAN NIELSEN
HanfoA Laboratories
ARTHUR W. FA.EUIALL
I@lverslvofWashington
ELLIE P. STEINBERG
A’gonneNationalLabormory
JEROME HUDIS
BrookbavenNational
Labommry
PETER C. STEVENSON
UnI~eraivofCalifornia
!Llvermore)
EARL HYDE
UnlveraiWofC ellfornia
(Berkeley)
LEO YAFFE
McGiilUniversity
CONSULTANTS
NATliAN BALLOU
Navalltadiologlcal
DefenseLaboratory
,.
JAMES DeVOE
University
ofMichigan
WILLIAM MARLOW
NauooalBureau ofStsndards
CW2-.7
LL74YC,l
CHEMISTRY
The Radiochemistry
of Aluminum
JOHN
E. LEWIS
Aluminum
Alcoa
Company
Research
Physical
.
and Gallium
Chemistry
New Kensington,
of America
Laboratom”es
Division
~”
Pennsylvania
Issuance
Date:April
1961
....—_’------
.—
Subcommittee on Radiochemistry
National Academy of Sciences —National Research Council
Printed
inUSA, Price$0.60.
AvaileMe fromtheOffice
of Technlcel
Services,
Department
ofCommerce,Washington
25,D. C.
FOREWORD
The Subcommittee on Radlochemlstry is one of a number of
subcommittees working under the Cmmlttee on Nuclear Science
wlthti the National Academy of Sciences - National Research
council . Its members represent government, tidustrlal, and
university laboratories in the areas of nuclear chemist~ and
analytical chemistry
The Subcoinmitteehas concerned Itself with those areas of
nuclear science which involve the chemist, such as the collection and d“lstributionof radiochemlcal procedures, the establishment of specifications for radi.ochemicallypure reagents,
availability of cyclotron time for service irradlatlons,”the
place of radi.ochemistryIn the undergraduate college program,
etc.
This series of monographs has grown out of the need for
up-to-date compilations of radlochemlcal information and procedures. The Subcommittee has.endeavored to present a series
which will be of maxlrmx’n
use to the working scientist and
which contains the latest available information. Each monograph collects In one volume the pertinent Information required
for radlochemlcal work with an Indlvi.dualelement or a group of
closely related elements.
An expert in the radlochemi”stry of the particular element
has written the monograph, follow=
a standard format developed
by the Subcommittee. The Atomic Energy Commission has sponsored
the printing of the series.
The Subcommittee Is confident these publications wI1l be
useful not only to the radlochemlst but also to the research
worker In other fields such as physics, biochemistry or medicine
who wishes to use radlochemical techniques to solve a specific
problem.
W. Wayne Melnke, Chalman
Subcommittee on Radlochemistry
iii
INTRODUCTJQIY
;
This volume which deals with the radiochemlstry of alumlnum and
galllum Is one of a series of monographs.on radlochemistry of.the
elements. There Is Included a review of the nuclear and.chemical
a discu~sion of
features ofpartlculaq interest to the radioche”rn’lst,
Droblems of dissolution of.a s~ple and,countlng techniques, and
IYnally, a collection of radiochemical procedures for the’element a’s
found In the literature.
Two considerations dictated the decision to treat aluminum and
gallium jointly In this monograph. First, and perhaps the most important, was the over-all slmllarlty In the chemistries of the elements.
Secondly, a. cursory survey ,o~tfieradl,ochend.calapplications of isotopes of the elements revealed appreciably more specific applications
of isotopes of gallium than aluminum and it was felt that neither
element warranted individual attention in ,separatemonographs.
The series of monographs will cover all elements for which radiochemlcal procedures are’perttnent. Plans Include revision of the
monograph~ perlodlca.lly as new.techniques. and procedures w,ur,ant. The
reader ig ,therefore encouragedt”o call ,to the atten~~Qn of the author
any published pr unpublished material on,theradio”c,hemlstry of alumlnum and gallium which idght,be Include,din a revised version of the
monograph.
.
CONTENTS
>1.
II.
III.
General Reviews of the Inorganic and Analytical
Chemistry of AlumLnum and Galllum. ..... ...........
1
General Reviews of the Radiochemistry
of Aluminum
and Gallium ........... ..................... ..“..... z
Tables
Of 180tOK8
......... ................ ....... 2
Iv.
Review of Those Features of Aluminum and GalliU
Chemistry of Chief Interest to the Radiochemist...
5
A.
Metallic State .............. .................. 5
B.
Compounds of Aluminum and Gallium ............. 7
c.
Gravimetric separations. ............... ....... 10
D.
solvent Extraction Separations ................ 12
1!%. Ion Exchange Separations. .............. .......17
F. Electrolytic separations. ......... ............ 19
v.
Dissolution of Samples Containing Compounds of
Aluminum and Gzillium........... ............ ....... 20
A.
Aluminum... ................................... 20
B.
Gallium ..................................... .. 21
VI.
CoUmting Techniques for’ use with Isotopes “of XIuminum and Gallium ................... .............. 22
A.
Aluminum Isotopes... ..... .................. .. . 22
B.
Gsllium Isotopes ....................0. ........ 23
VII.
Collection
Procedure
Procedure
Procedure
Procedure
Procedure
Procedure
Procedure
Procedure
Procedure
Procedure
of Detailed Rad&ochemical
Procedures.. .
1 .................... ...................
2 ............... ........................
3 ... ....................................
24
24
25
26
4....................................... 27
5....................................... 29
6....................................... 31
7....................................... 32
8........................................ 35
9....................................... 39
10...................................... 41
v
.
The kadiochemistry
,,
,“ ~.
.$
:
.
of Aluminum
,:
and
Gal ium
JOHN E. LEWIS
Aluminum Company of America
Alcoa Research Laboratories
Physical Chemistry Division
N6w Kensington, Pen~ylvania
.
I.
(1)
(2)
GENERAL REVIEWS OF THE INORGANIC
STRY
OF KUJMINUM AND GALLIUM
N. V. Sidgwick,
“The Chemical
p6unds, “ oxford
University Press,
.
London
W. R. Schoe\ler
and, A. R. POW1l,
“The Analysis
Minerals
Hafner
“(3)
AND ANALYTICAL
Elements
Publishing
“W. F. Hlll&rand,”
Ccqrpany, New York
G. E.’ F.
“Appiied
tion, John Wiley
(5)
Lundell,
‘H. h.’ Bfigh”t and
Inorganic
Analy’tiis,‘r 2nd E“dL,,,,
and SoIiS, I“nc., New Yotk “(1953).’
“properties
Laboratory
Report
(1937”), Lith6print
Ann Akbor, “Michigan
Verlag
Edition
(1944).’
1
of Gallium, ” Argonne
No. ANL-4109
Einecke., “Das Gallium”
Leipzig
of
.:.’
W. D. Wilkinson,
,,
Etich
(1950 ).
(1955).
.,,
.
National
Their com-
and ores o f the Rarer:,Elements, “ 3rd Edition,
J. I.” Hoffman,
(4)
-d
CHEMI-
(1948).
von Leopold
Voss;
by J. ‘W’.Edwards,
‘,”,
.
(6) J. Dolezal, V. Patrovs~.
“Analytical Chemistry
1517
II.
Z. Sulcek
and J. Svaata,
of Gallium, ” Chem. Listy —
40,
(1955).
GENERAL
REVIEWS
OF ~
RADI~ISTRY
OF AIUMIIQUM AND
At this writing, the author 18 not aware of any
,.,,.
., .;
,.
publication “&ich ‘qualifies to be classified as a review
of the radiochemistry
ever,
a series
OF either
aluminum
of articles, authored
associates, ‘1’2’3’4) pertaining
Al 26 isotope,
.
long-lived
. ... .
category.
III. TABLES
by R,ightiire and
special
mention
,...
of
in this
,,
OF ’ISOTOPES
,..
The most
field of aluminum
significant
recent
iadiochemist~
et””al., (l)ofWe
the meta8t@ble
until
How-
to the identification
.
deserves
,.,
.,,
Shnanton
or gallium.
~ong-l~ved
the time of the discovery
devoid
Iments.
half-lives
me
A126,
is~iic
AS tfie autho&
tiirit””:outi,
the
is,otope for tracer
A128
‘
’with
in 1954, ,aluminum -s
.. . .
‘,
of a ,.
suitxle
of,the
to the
was the ‘diec”bve~, by’
,6.6 sec.. isotope.;
only element
,,-
contribution
exper-
aqd AI*9 isotopes
-e
sufficiently long to permit their use in specific applica. ..
tions such “as activation smaiysis’, but this use has been
confined
“to laboratories
fortunate
enough
irradiation, ,facilities.
,,
currently
a number. of manufacturers
are offering
ticipated
laboratory
size nmtcon
that short-lived
isotopes
2
to-have
s,ourcea and it
their own
in an-
such as Al*.a E@l A129
will
find increased
application
in future radiotracer
in-
vestigations.
T&le
ISOTOPES
Half -Life
. 13
I
OF ALUMINUM*
TYPe of
Decay
Energy of
Radiation
Some
Typical
Modes
of
Formation
Bee.
-8.5
1.3a -7.l
7.6
BeC.
6.6
Oec.
~g24
(p,n)
s+
3.2
ie
(p,n)
~+
3.2
Mg25
(d,n)
(d,2n)
M926
ec
axlo5y
@
1’
100%
Mg25
1.16
1.83,1.14
@‘Y
2.86
1.78,1.27
:Pj
P 31
6.56 tin.
●
Data obtained
(d,n)
(p,n)
(n,2n)
-----
Abundance
(Stable )
2.27 min.
M926
A127
B‘Y
2.5,1.4
1.2a,2.43
from the following
Al
Mg
(n,7)
(d#p)
(n,U)
(a,2P)
(a,p)
sources:
(A)
Friedlander, G. and Kennedy, J. W., “Nuclear and
Radiochemistry,n
John Wiley and sons, Inc., New
York (1955).
(B)
Strominger, D., Hollander, J. M. and Seshrg,
“Table of Isotopas,” Reviewe of MO&!rnPhyslcs
No. 2, 585 (1958).
G. T.,
3Q,
Table
ISOTOPES
of
Decay
Type
Half -Life
2.6
G=”
min.
6+
~a65
15
min.
:+
~a65
8
min.
;+y
Ga66
9.4
hrs.
Y
D+
II
OF GALLIuM*
Energy of
Radiation
-5
0.97, 2.2,3.6
2.2
0.052
----0.092,0.114
4.14
-----
ec
~a67
78
G=68
Ga69
~a70
Ga71
~a72
hrs.
68
min.
60. 5% Abundance
“(stable)
21.4
min.
39. 5% Abund-ce
(Stable)
14.2
hrS.
‘r
ec
5.0
8
*
hrs.
min.
Data obtained
(A)
\
(B)
0.09 to 0.9
1.88
zn64
zn64
(pcn)
(d,2n)
Id, n)
Zn”
(d,2n)
~63
(p,n)
(a,n)
~n”
(d,n)
(d.,
2n)
1.10
Zn’8
~u65
*7O
1.65
Ga69
1’
0.17,1.04
Ga69
G~~2
(n,T)
(d,p)
(n,p)
(d,a)
@-
0.6, 0.9,
1. 5,2.5,3.1
0.84,2.508,2.491
plus
others
1.4 (to Ge73m=)
1.1,2.0,2.65
0.60, 2.3,0 thers
;+
ec
?’
@-
‘r
~a73
~a74
0.83 to 4.Q3
-----
Some
Typical
Modes
of
Formation
P@-
from the following
~a71
g~’7~
~e73
=74
Ge74
(a,n)
(d,a]
(d,p)
(n,y)
(n,p)
(n,p)
(n,p)
(n,f)
sources:
Friedlander, G. and Kennedy, J. W., “Nuclear and
Radiochemistry, “ John Wiley and Sons, Inc. , New
York (1955).
Strominger, D., Hollander, J. M. and Seaor9,
G. T.,
“Table of Isotopes, ” Reviews of Modern Physics —30,
No.
2, 585 (1958).
REVIEW OF THOSE FEATURES OF ALUMINUM AND GALLIUM
ISTRY OF CHIBF INTERBST TO THE RADIW13$MIST
IV.
A.
Metallic
State
Alumlnum
and ranks third
trast,
gallium
although
is the must
in abundance
widely
with being
occurs
sandtha
of one per cent)
liquors
during
in trace
aluminum
brief
is unwarranted,
mention.
in either
point
or solid
of approximately
exhibit
a blue-greg
pxn.ue
acquirea
coloration
to air, which
further
oxidation
Gallium
The
3%.
properties
Selected
in Table
111.
for their
volume
deserves
of its low -lting
with
a thin protec-
oxide
and gallium
film upon ex-
ability
to retiist
attack.
is remarkable
supercooling and will remain
of
may be encountered
Both aluminum
impervious
and chemical
on freezing.
gallium
alumina.
appearance
of gallium
associated
accounts
even at ice temperatures.
to yield
Bo12h solid and liquid gallium
29.8°C.
relatively
quanti-
in the caustic
state because
tive oxide film on the surface.
quickly
of gallium.
at a few thou-
of the physical
the appearance
Germanite
significant
of the bauxite
In the laboratory,
a liquid
but
concentrated
a description
1.5 x 10-3%),
source
(estimated
(B.1%)
By con-
in nature.
known
in bauxite,
become
of all metals
(abundance
distrtiuted
anmunts
proceselng
while
scarce
the richest
Gallium
ties of the element
abundant
of all the elements.
is relatively
it occurs
is credited
CID3M-
in its ability
indefinitely
GalllUm,
change
in a liquid
llke bismuth,
on solidification
of alumAnum
to undergo
and gallium
state
expands
is about
are listed
Table
III*
Property
Atomic
Aluminum
Number
Mass Numbers,
Stable
Isotopes
Density
of Solid at 20”c, g/cc
Melting
Point
“c
Boiling
Point
‘c
Ionization
Crystal
*
13
31
27
69, 71
2.70
ev
ti3, ~
Aluminum
as &etals
commercially
.2070
5.9e4
,, 6.00
,0.50
0.62
and, in general,
creasing
lution
aluminum
dissolve
aluminum
Foster(5)
in.alkaline
be-
media.
increases
acids
“with
in concentrated
Increased
HC1 but the so,.,
with the addition of
salt.
Caustic
so-
readily.
sustains
of two-thirds
elements,
in.
and temperature, except in nitric
,.
relatively passive.
Superpure
ie difficultly
reports
and
in dilute mineral
HN09 or a trace of mercury
but hot aqua regia
mixture
slowly
rate can be markedly
Gallium
rate.
is ioluble
remains
Johh Willey
are amphoteric
the rate of dissolution
dissolves
concentrated
lutions
aluminum
acid concentration
acid where
aluminum
and gallium
in acid and as nonmetals
pure
29.78
2270
.
Therald Moeller, “Inorg~c
CheQ)iStW.”
Sons, Inc., NeW York (1952).
having
5.93
659.8
Potential,
Radius
Gallium
soluble
dissolution
rapid
solution
concentrated
6
HzSO*
in mineral
acide
at a respectable
of gallium
in a
and one-third
,:
per-
chloric
acid (72%).
trolytic
solution
num container.
solves
Foster
of gallium
in strong
Although
in hot nitric
alkali
gallium
states
is recognized
of gallium
are of primary
chemist.
Similarly,
.tiivalent aluminum
countered
in procedures
While
pounds
with
pertinent
aluminum
various
those compounds
standpoint
which
l’he hydroxides
are of interest
hydroxides
show l~ted
but
cipitates
to form aluminates
tannin,
employed
practice,
(hydrated
alkali hydroxides
is sometimes
ammonium
to obtain
form numerous
reagents,
only
from a radiochemical
precipitate
oxides)
alu-
upon neutral-’
salts of the elements.
in excess
completely
nature
anznonium
dissolve
the pre-
of the hydroxide
precipi-
and precipitant
such as
and sodium
a more granular
it is customary
com-
and gallates.
objectionable
bisulfite
work.
and oxides
volubility
hydroxide
tates
en-
here.
of the trivalent
The gelatinous
to the radio-
to radiochemical
and alkali hydroxides
izing acid solutions
in
the trivalent
is normally
and inorganic
will be considered
and gallium
dis-
as existing
interest
and gallium
organic
Ammonium
gallium
and Gallium
Hydroxides
minum
acid in a plati-
(i.e., +1, +2 and +3),
COmPO unds of Aluminum
the elec-
solutions.
compounds
B.
discuss
As in the caae of aluminum,
readily
three valence
and Stumpf(6)
thiosulfate
product.
to uee aluminum
7
may be
In analytical
and gallium
hy-
droxides
only as intermediate
products
sequence
since
are capable
a host
the hydroxides
of contaminating
While
types
described
and gallium
by the general
the radiochemist.
cupferrates
or organic
and quinolates.
provide
products
special
care must be exercised
to prevent
oxide by traces
are of interest
involving
the ig-
of the oxides
~
is
of 1000”c to
nonhygroscopic.
in igniting
the lose of gallium
organic
as b
from the reduction
of unconsumed
to
the
such as
in excess
are completely
(GaaO) resulting
Mao and me09,
precipitates
at temperatures
which
down
of the
are frequently
Ignition
performed
suboxide
w,
procedures
ueually
of gallium
formulas
The sesquioxides
of hydroxides
form oxides
(A1203 end GasO=)
final product, ip gravimetric
nition
of carrying
elements.
aluminum
only the sesquioxides
in an “analysis
compounds
volatile
of the sesqui-
carbon.
Halides
T’& halides
of gallium
are hydroscopic
and undergo
The dichlorides
and dlbromides
temperatures
metal.
to yield
ie the exception)
in aqueous
disproportionate
GaCla
trihalides
ia of prm
solution.
at elevated
plus
free
interest
in
radiochemistry.
Anhydrous
dry hydrogen
relatively
hydrolysis
the respective
of the trihalides,
analytical
(fluoride
chloride
GaCls,
fonued by reacting
or chlorine
low temperature
gasea,
(b.p. 201”c)
8
the metal
volatilizes
and sublimes.
with
at a
This
property can be used to advantage
compound
or separating
the loss of gallium
evaporations
during
it from lees volatile
as the chlorides
of acid solutions
the ignition
exists
various
organic
solvents
anion exohange
resins
form a similar
chloride
general
similarity
their reparation
ion exchange
drogen
such as XX-1.
tie halides
Like
is produced
chloride
sublimes
of tM
chloride,
into
adsorbability
Aluminum
from the
of the elements
solvent
by
does not
and ~s”depature
of aluminum,
its gallium
by reaction
or chlorine.
at approximately
Hydrated
permits
extraction
and
,anhydrous
of the metal with
gaeeous
hy-
Alclg
readily
and
volatilize
chloride;A lClg”6Hao,
in concentrated
hydrochloric
tation
can be used to “separate aluminum
C)
ie of pri-
17B°C.
alumlnum
(See Section
ALCla
counterpart,
attack
ryllium.
loss may occur
technique.
interest.
A1C19
and chows strong
in the chemietry
While
nil during
is extractable
from each otherv ia
Among
mary
ion which
complex
species.
the
compounds. (5)
bearing
acid solution
ae the GaCl~
of purifying
presumably
of the salt,
of gallium
In.a hydrochloric
gallium
aa a means
resists
acid and A1C19 precipifrom iron and be-
.
Sulfides
.,
The literature
gal~ium,
namely
of altinum,
GaeS,
AIzSS..
li~ts three
stable
sulfides
of
Gas and “Gazsg, and only one sulftde
The”ae sulfides
9
form by reacting
&
~
‘
metals
with hydrogen
temperatures
sulfide
and are of little
Aluminum
their
solutions
small
amounts
weakly
HQS .
and gallium
Arsenic
Gravimetric
amounts
with
echeme.
tanium,
method
chemical
and gallium
ration
seine only
AlC13.6HSO
vides
of the matrix
aluminum
such that separation
by this
of impurity
involving
snalysis
element
step in radio-
of interest.
may carry
from a cold hydrochloric
In
in alumirequires
the sepa-
The renmval
of alumi-
the voluminous,
down elements
suggested
the precipitation
which
frequently
because
A procedure
product
elements
to facilitate
is unsuitable
precipitate
a crystalline
iron, ti-
etc. accompany
as an intermediate
by activation
or entrainment.
Havens(’)
sepa-
schemes.
num as the hydroxide
tation
“get-
as
“RaOg” group
including
rare earth metals
of the element(s)
gelatinous
by
are precipitated
of elements
A number
The determination
the removal
precipitable
is an excellent
auznonia in the familiar
analysis
num and gallium
from
of gallium.
in the precipitate
usually
adsorptively
Separations
zirconium,
and gallium
when
HOWeVef,
sulfide.
elements
in particular,
Both aluminum
ration
do not form s~lfides
containtig
sulfide,
at elevated
to the analyst.
of ga”llium can be separated
acid solutions
hydroxides
interest
are gassed with hydrogen
ter” for small
c.
or stiifur vapors
by coprecipiby Gomh
of aluminum
acid-ether
and
as
solution,
is comparatively
pro-
free of
copracipitated
contaminants.
in separating
alumlnum
Aluminum
a dilute
acetic
(NH4)aHP04
will be
procedure
can be employed
from gallium.
may be precipitated
acid-sodium
but elements
acetate
as the phosphate
solution
from
with exceae
such as iron, titanium
and others
found in the precipitate.
Phenyhydrazine
parating
*ich
~is
aluminum
accompany
is a useful
from divalent
precipitant
iron and other
it in the ammonia
for se-
elcsnents
group precipitation
pro-
cedure.
8-hydxo~quinoline
tatively
precipitates
in the pH range of”4.2
A1(CBH61!?O)S, can be weighed
quioxide,
acidic
AleOg.
or alkaline
contaminating
cipitated
media
el~ts
has become
6 and 9 in section
H~S04
ing an excess
following
um camphorate
is also pre-
3, 5,
gallium
(approxtiately
The 9alliUm
quantitatively
10%by
volume)
is collected
us-
as GaeO=
of the cupferrate.
cobalt
reports
tbe separation
and others
additions
Gallium
of possible
(See Procedures
will precipitate
solution
Hopkins(g)
zinc, cadmium,
Gallium
in either
and its use in radiochemical
widespread.
of reagent.
ignition
knowledge
to the ses-
VII)
Cupferron
from dilute
or ignited
is” desirable.
quanti-
The precipitate,
is not specific
and prior
by this reagent
aeparationa
to 9.8.(8)
directly
The method
aluminum
to acetic
with camphoric
from
acid or sodi-
acid solutions.
can be separated
Kl
of gallium
from aluminum
and chrom-
ium by precipitation as the ferrocyanide.
precipitate
witi” gallium
separation.
Following
gallium
D.
removed
reprecipitated
solvent
from acid solution,
ignition
tate, the iron can.be
Zinc,
by
familiar
technitiea
.,
and g.alliqm form extractable
Steinbach
chloroform
at PH’S of 4 and 2, res~t,ively.
,:
Void
of the gallium
and gallium
et al.(ll)
crystals
to distinguish
were
g~llium
Bolomay
and Wish(12)
at pH 5.5 by 0.02M
that aluminum
oroacetone
solution
.by microscopic
the extraction
TTA in benzene.
..
Eshelman(13)
extracted
pH 5.5 to 6.0 with
solution
and gallium.
(TTA)
(TTA) in 4-methyl-2-pentanone.
an acetate-buffered
cupferron
of
of alu,ob-
from an acetate-
O-I-M 2-thenoyltrifluAlternative ly,
of PH 2.5 to 4.5, c0ntainin9
,,,.
with 4-methyl-2-pentanone,
.12
90%
frop aluminum.
report
is selectively
.
to extract
of aluminum
identified
in
,,
used acetylacetone
b.
Thenovltrifluoroacetone
,.,.
..’
buffered
by.acetylacetone
from 61% HC1 solution
Ga-acetylacetonate
chelates’
Frqiser (10) de~Crfie. tbe
-d
of aluminum
sened
and the
Separation
extraction
min~
precipi-
Acetvlacetone
acetylacetone.
exanQnation
prior
as the hydroxide.
Extraction
..-
Alym$num
with
requires
of the ferrocyanide
1. ,.chelate Complexes
a.
which wmld
was used.
Morin (3,5,7,2,4-pentahydroxyf lavone)
c.
Morin
acidic media
amyl, butyl
d.
reacts
to form complexes
and cyclohql
lective
with
aluminum
and gallium
that are extractable
in
by
(14)
alcohols.
8-Qu inolinol
Although
complexes
with both
(Oxine)
aluminum
form extractable
the extractions
8-quinolinol,
and are subject
and gallium
to contamination
zwe not se-
by interfering
iom.
Luke and Campbell
germanium
6N HC1,
and germanium
determined
dioxide
metrically
cyanide
solution.
in tbe yellow
Kambara
for extraction
Gallium
oxinate
can be extracted
from
from
photo-
extract.
discuss
the theory
by chloroform.
report
completely
(PH 3.0 to 6.2) salt solutions
solutions
was determined
and Hoshitani(16)
‘Moeller “&.ndcohon(17)
oxinate)
extraction
oxine-hloroform
of aluminum
and
by ether extraction
followed by an oxine<hloroform
alkaline
gallium
that gallium
(as
from acetate-buffered
by shaking
with chloroform
of 8-hydroxyquinoline.
Lecroix(18)
could be separated
as the oxlnate
demonstrated
from 104 parts
at pH-Z
into
that one part
of aluminum
,,
chloroform.
of gallium
by extraction
e.
Cupferron
@mmonium
droxy lamine)
The extraction
chloroform
has been
Salt of N-nitrosopheny
of alundnum
investigated
as the cup ferrat
by Meunier (19) and Ba
and Furst. (20)
f.
Sodium
Diethyldithlocarbamate
Cherniko
and Kobkina(21)
of the galliUIU complex
ing excess
acetate
The extraction
at pH-3
to preclude
of aluminum
with the above reagents
quantitative
lar reagent
2.
for a specific
via an ion pairing
of gallium,
partner
of gallium
halides
selective
a
to refer to t
the suitability
of metallic
elements
complex
of a F
is made
in the aqueous
Ae an example,
in the c
is that gal”lium forms an ext
via incorporation
Milner
for
application.
mechanism.
of the ion pair
of the co
via complex
ia cautioned
of a metal
the consensus
able complex
extract
Complexes
The extraction
ble by the formation
decomposition
Is not necessarily
.
to determine
Ion Aseceiatfon
the
into a ethyl acetate en
and gallium
agd the reader
ginal publications
report
(#,
of the metal
in the ani
GaC14-).
et al. ’22) investigated
from acid solutions
and obser,ved that the chloride
the extracta
with organic
was extracted
ly than either the broriide or iodide.
14
sc
more effl
It was also
fou
that extraction
of the chloride
as the customary
diethyl
red in their wrk
gallium
involving
was recovered
after buffering
ate buffer
by precipitation
(III) and Ga
extraction
While
this procedure,
indicated
The Al
Au
acid
form-
of chloride
organic
solvents
aluminum
in the following
(111) showed negli-
complexes
of gallium
considerable
to separation
is excellent,
by
as
tabulation:
HC1
Ethyl Ether
7M
HC1
Isopropyl
3M
HC1
Tribu@rlphosphate
(III), to mention
from HC1 solu-
has received
Per Cent
Extraction
elemsnta
from 20M
respectively).
is not amenable
the extraction
the extrac-
complexes
(III) and Ga
6M
Additional
with camphoric
(III) as fluoride
Aqueous
Ga III
l%e
investigated
(i.e. 0.2% and <0.05%,
into various
attention.
mixtures.
formic acid-ammonium
have
and Herman
The extraction
tions
with
ketones
but ether was prefer-
gallium-uranium
the solution
HI’ into ethyl ether.
gible
solvent,
using
of PH-3.3.
Bach
tion of Al
ether
was as efficient
Ether
such as Sb
(V), As
a few, are likely
Reference
97
(24)
>99.9
(25)
99.9
(26)
(III), Ff3 (III) and
to extract
with
the
gallium.
The extractabili~
into ethyl ether has been
of a number
investigated
15
of metal bromides
by Bock et al.(27)
While
Al
tent,
95 to 97% extraction of gallium
(III) was observed to extract
solution was found.
the gallium
nants
would be accompanied
The extraction
or gallium
by a variety
(V) and Fe
extraction,
of contami-
(111).
and galliti
of aluminum
has not looked promising.
ex-
from 5 to 6~ HBr
As is the caae of chloride
such as In (III), Sb
of aluminum
to a neglig~le
Kitachara(2a)
as Iodides
found no extraction
from 6.9M HI solutions
into ethyl
ether.
B~k(*9)
h as made
of the extraction
a function
of metal
of NH4SCN
mum extraction
that best
tration
thiocyanates
concentration.
(approximately
(III) exhtiited999%
gested
results
In the aqueous
are extractable
amyl alcohol.
Sundaram
butyric
extraction
ethyl ether
(III) showed
from 7MBN&cN.
when
as
a maxi-
while
Ga
It is sug-
the HC1 concen-
Is 0.5M.
has obsemed
lium benzoates
into
Al
are obtained
phase
Investigation
19%) from 6& BN4SCN
extraction
Johnson
complete
a comprehensive
that aluminum
by ethyl
ecetate
and Banerjee(31)
report
of aluminum
by chloroform
and gal-
or butyl
essentially
from aqueous
acid at pH of 9.3 to 9.5.
White(32)
reported
complete
extraction
of Ga
(0.11.i
(III) from 7M’Hc1 with tri-n-actylphosphine
oxide.
in cyclohexane. )
(III) was af-
fected
complete
from 7~ HC1 using
n-hexylphosph ine oxide.
company
or
aluminum
in both
extraction
of Al
a O.I.M solution
A variety
extraction
16
of tris-2-ethyl-
of other
elements
procedures.
ac!-
The majority
section
on solvent
of the material
extraction
presented
was taken
in this
from the book by
Morrieon and Freiser. (33)
E.
IOn Exchange
separatlon~
The ion exchange
is ideal for
trace element
radiochemical
work.
approach
partitions
Aluminum
‘separation from each other
from a host of other
The investigator
exchange
influence
technique
elements
by ion exchange
between
(Dowex-50
resin
an anion or cation
will
likely
Ti and Fe
reports
(III) in Dowex
was employed
by Kejima
and aluminum.
Kcl mixture
to Al
of Al
and the aluminum
In recent years,
with
lR-120 column
eluted
with
removed
anion
in uee for effecting
1.31Q
(III) from
2N HC1.
Ti-
in the H + form
to separate
iron
a O.lN KI-O.15N
with
2N HC1.
exchange
elemental
17
with
(III) with the same acid
and Kakihana(36)
The iron hs
a
Iridium was
was removed
50x8 by SlutIon
An Amberlite
ex-
by elution
HC1 solutions.
the separation
and iron elute prior
concentration.
a cation
in H+ form) to effect
iridium and germanium
concentrated
Strelow(3’)
increaaed
to
techniques.
conditions
eluted with 0.4N Hc1 and the gallium
tanium
in
are amenable
and Sandmann ’34) utilized
of gallium,
increasing
Hcl.
required
his decision.
separation
with
separations
and each in turn can be separated
and experimental
Klement
change
often
and gallium
has to choo~e
procedure
to c@.mical
procedures have
.
separations pre-
viously
assigned
metallic
tively
to cation
elementB
charged
complexes
exist
complex
are strongly
and Nelson(37)
sorbability
discuss
of Ga
exchange
procedures.
(or may be converted
ions in aqueous
adsorbed
in
to) as nega-
solution
by various
detail
Many
and these
Kraus
resins.
the mechanics
(III) as the anion complex,
of the adGaCIA-,
from
that Al
(III)
Hcl solution.
Iccaus, Nelson
and smith(3a)
undergoes
negligible
exchanger
of the polystyrene-divinylbenzene
(III) exhibits
adsorption
showed
strong
an HC1 concentration
adsorption,
of 7M.
(III), In (III) and T1
the aid of Ga67,
on Dowex-1
(strongly basic
type) while
the maximum
TW
separation
(III) on Dowex-1
occurring
of Al
Al
[Al (III) appearing
first 20 ml. of eluant
(III) following
50
❑l.]
while.Ga
was used
(III) was eluted witl~HCl
to remove
T1
basis
resins
from halogen
for specific
exchange
media
behavior
in the next
and 4M HC104
separations
end Nelson
fromadsorbable
as the
elements
(40)
(41), have
of the majority
(HC1 concentrations
on anion ex-
acid media has served
such as zirconium ‘39)and others.
Kraus
in the
(111).
The fact that Al iIS not adsorbed
change
with
(III) and In
(III) were eluted wiiih 7gHcl
and In
at
(III), Ga
was observed
In114 and T1204 tracers.
Ga
ranging
extined
of elements
the SIlioll
in chloride
from 0.1 to 12M).
Faris, (42) in his investigation of the adsorption charac.
teristics of some fifty elements on Dowex 1-X1O resin
18
-
showed
67
that Ga .[111),‘as Gis ,,tracer, ehibits
adsorption
from “1, 2 “&d 4~ “~.
coefficient
Al
of approximately
5.5 for Ga
(III) shows a distribution
1.5 for lM HF &ich
He retirti
a dietributlon
(III) in 0.4M ~.
coefficient
decreasee
.negligtile
to zero.at
of approximately
approximately
12M
m?.
Marinaky
Kruger(+)
and Eichler(43)
give specific. ion exchange
tion VII] for separating
produced
and GrUVermSn
gallium
VII include
carrier
isotopes.
procedures
free amounts
Procedures
the use of ion exchange
and
(see Sec-
of CyClOtrOn
7 and 10 in Section”
in the separation
of
~126,
..
,,
F.
Electrolytic
Separation
The cathodic
aqueous
solutions
electrddeposition
of its salts
provides
an efficient
elements
such as alumifiumand
from aqueous
media.”
nmans
while
(GaClg, Gae(S04)g,
of separating
sodium which
other
&laments,
iridium, zinc and lead to mention
gallium,
the nuntmr
by controlled
electrolytic! methods.
for example,
elements
can’be
and other
A qm.ntitative
recovery
difficult
not a serious
lbdtation
Electrolysis,
in conjunction
to achieve
in most radiochemical
with
used procedure
from
do not deposit
elactrolysia
by electrolgaiia may prove
is a frequently
gallium
fractional
for purifying
19
from
NaGaoa)
a.few, may codeposit
of interfering
potential
of gallium
~~
wiEtI
limited
seleotive
of gallium
but this iS
application.
crystallization,
gallium. ~45)
v.
DISSOLUTION
AND GALLIUM
A.
Aluminum
OF wLES
CONTAINING
COMFOUNDS
OF ALUMIHIJM
ores and Refractory Aluminous Materiala
1.
Bauxite
acid mixture.
bauxite
In caaea where
fusion procedures
borax
fuaion~
conducted
(46)
ia ob-
is to be determined
la usually
mind.
For inetance,
mining
silicon,
media
via
in
familiar
attack
in acid
of a solution
objective
ia Interested
of the aanple
may result
formation
AlloYa
by the ultimate
in
in deter-
ia desirable,
in an incomplete
to ailic,a and silicon
of
procedures
can be diaaolved
and the choice
if the analyat
since acid decomposition
Solution
or carbonate-
are familiar
and Aluminum
dictated
an alkali
tion of the silicon
Biaulfate
and ita alloys
hydroxide
hydride
ia
oxide.
solution of Aluminum
procetie
aalta
dissolution
in platinum
aluminum
Aluminum
silicon
aillca
silica
(aodiuiu carbonate”, alkali pyroaulfate
ia to be recommended.
or alkaline
when
of foreign
refractories,
etc.)
for diaaolving
by an HF-HES04-HN03
method
and the presence
or calcined
2.
readily
This La a preferred
to be eliminated
jectionable.
ia attacked
losaea
oxida-
due to
may be encountered.
aluminum
mstal proceeds
well
in Hcl,
$
HF and otier binary
by HzS04,
halogen
HH09 and other
acida.
common
The attack
inorganic
20
of the metal
acids used aepa-
is S1OW, but
rately
by the addition
agent
of a pinch
in the industry
ndxture
acida
solution
reagenta
ra~er
in dry hydrogen
formation
of anhydrouB
relatively
The reaction
attacked
aluminum
by’organic
chlorine
chloride
(slightly
metal
regia or sodium hydroxide
IS a
of organic
by heating
or oxygen-free
resi6ta
whiah
above
the metal
with
the
mblks
at a
180”c).
attack by HC1 but
salt may be used to accelerate
high purity
the metal
re-
utilized.
low temperature
High purity
A etandard
B1OW and solution
la readily
chloride
can be hastened
salt.
for dissolving
is not cu~tomarily
Aluminum
B.
of mercury
of HC1, HNOS and HaSo4.
1s, in general,
mercury
in these media
the action.
are also effective
a
Aqua
reagents
for
aluminum.
Gallium
1.
“&es and RefractoW
GalllUm
eximte
CQmPou.nd?l
in trace quantities
of ores such as germanite,
zinc blende.
bauxite,
AS in the case of aluminum,
tacked by acid or acid-mixtures,
flux fusion procedures
jected
provided
temperature
during
the oxide ham been calclned
1000”c,
and
the ores are at-
or the conventional
of gallium,
in alkali hydroxide
to high
iron ores
salt
may be utilized.
The sesquioxide
soluble
various
in a number
fugion procedures
Gago9,
it has not been
drying
at temperatures
are necessary
ble.
21
is easily
operations.
in excess
to render
mbIf
of
it solu-
2.
Gallium
and Gallium
The volubility
sent in aluminum
in commercial
separates
as globules
chloride
which subll.mes. LMWAS
,,
such a procedure for separating
23O-255”C
(b.p. GaCl~
Gaclg
and
the metal
soluble “in HC1.”
most
readily by
aluminum,
gall~um
to form the anhydrous
s.nd BrldgTMUUI(48~ adopted
gallium
from in&ium
‘“
and
in a stream of dry chlorine
at
- 215-220”c).
,.
,.
VI.
pre-
in that
solution
in ma~sium
Like
with dry HC1 or” chlorine
zinc by ualaklllzing
in solid
is attacked
hydroxides.
whether
is different
are “not readily
gallium
aqua regia or alkaline
exists
acid, “tine
which
In generai,
of gallium,
alloys,
aluminum, gallium
in hy&ochloric
rea&
behavior
or magnesium
dissolves
will
A11OYS
COUDlTD9G TECHNIQUES
AND GALLIUM
FOR USE WITH
ISOTOPES
OF ALUMINUM
,“
A.
Alumlnum
Isotopes
:
~
“-
.,
..,’.
to the table of alumlnum isotopes (Sec.,.
,.
.,
tion III) it is obse~ed
that the half-lives fall Into two
Refering
,’.
of half-life less than one hour,
,,,
“.’
,’
snd one isotope with an extremely long half-life of approxi,.
mately 8 x 105 years.
For purposes of this discussion, only
categories:
six isotopes
the isotopes
of mass
Al&num2B
~- emission
26, 28 and .29 will be considered.
.. .
2.3
@l/2 approximately
,, min.) decays
“ by
(~- 2.86 mev.’j followed
by the emission of a pri,.
mary game
ray of 1.78 mav.
While this isotope “can be assayed
,,.
,.!.
by a conventional Geiger-Mueller
counting procedure, a ganmIa-
22
ray acintiilktion
ing counting
Gu&nn
:e,pectrometer provides
procedure
in view or t-
and Wagner ’49) describe
scheme
for determining
ploying
discriminat-
short half-life
an instrumental
aluminum
a scintillation
a rapid,
in a variety
involved.
neutron
analysis
of materials
em-
apectrcmeter.
,.
Al&num29
ganma.raya
devices.
(tl/2 = 6.56 min.) “=ta
and is amenable
Spectrometers
to advantage
interfering
,.,
measuring
&d
detection
and propaitiorial &ounters”may
be used
its ratilat”i.on
in
activities.
!rhe;giound’ etate A126
,,,
,.,
beta
to assay by conventional
for discriminately
the presenceof
boh
isotope,
a half-life
with
timated .at apprQxiinately 8 x 105 years, (2) ~ts
,.
es-
1.16 llMSV-
,.
positrons,
EC radiations and gamma rays with energies of 1.83,
,,,
.’
follotirig
2.97 and 1.14 mev.
Kohman et al. (4)’de~cr~e’tk
assay
procedures:
..
(1)
Routine - “positrons by Geiger and
proportional
counting procedures.
(2) specific - gamma scintillation
a~ctrometer
for. counting: tbe 1.8?msv. gamma ray.
(3) Absolute - measurn poeitrwm
in 4
pi counter.
..
. .
.
..
(S~le
efialosed in aluminized
exclude
electron-capture
Mylar
foil ’(1.O mg./cm.2)
. ,. \
radiation.)
.
B.
Gallium
.
Isotoms
It iS seeh
galllum
to
isotopes
frOm Table
II that the m@ority
decay with P “and y ray emissiohs
‘sufficiently
energetic
proportional
and “scintillation counting
which
to be assayed by’ conventional
procedur&B.
.,
23
of
are
Geiger,’
VII.
COLLECTION
OF DETAILED
IU4DIOCHEMICAL PROCEDURES
Procedure
1
Gallium
Source:
mental
Ernst Bleuler
and George
Nucleonics, “ Rinehart
J. Goldsmith,
and Company,
“Experi-
Inc., New York
(1952) .
Reagents:
HC1
- 5.45M,
,HNos
Cone.
NH4 OH - dilute
Ether
H=S
Irradiation:
clea
cu target
10 mg. or lees.
1 - DiaOolve
Step
2 -
target
3 ml.
cone.
(Caution:
Step
3 - Saturate
shaking
mtiutes.
Final
- approximately
Activity
Step
COIIC.
(thin foil) bombarded
5 microampere
for about
Add
0.3M,
in 1 m+. cone.
sample weight
200 counts/aec.
HNOs.
HC1 and evaporate
lowheat
with a parti-
to -as.
to avoid bumping.)
25 ml. ether with
in separator
25 ml. 5.45~ Hc1 by
funnel.
save both
ether
and acid portions.
Step
4 - Cool evaporated
to saturate
Step
5 - Extract
remove
in clean
ether
er because
with
three
Cu and Ga.
1 ml. portions
Combine
ether
r3eparatory funnel.
solution
cu which
and add the acid used
ether.
to remove
fractions
6 - Extraat
the
said solution
of ether
Step
residue
with
may have
10 ml. 5.45M Hc1 to
dissolved
of tie water which
the ether.
24
in ether
is dissolved
layin
Procedure 1 (Continued)
step
7 - Evaporate
ether
solution
to dryneaa
for gallium
aaeay.
Skep
8 - Evaporate
aqueous
solution
to dryness;
dissolve
C!u salt in 15 ml. 0.3~ ECl and saturate
solution
wifi HsS.
Step
9 -
Coagulate
copper
sulfide
precipitate
and filter on fine filter paper.
hol,
followed with
by heating,
D=
wltb
alCo-
ether.
Procedure
2
Gallium
Source:
Same as for Procedure
Reagents:
See Procedure
Irradiation:
several
Deuteron
microampere
1.
1.
btiardment
minutes.
of zinc foil target
ActivLty
for
- approximate ly 200
coumts/sec .
The chemical
gallium
except
activity
precipitated
with ~am)
ether
duplicates
that the tsrget
is again rmmved
processing
of the target
steps
is dissolved
by solvent
from neutral
directly
extraction
solution
and the ZnS is assayed
fraction containing
1 through
gallium
for assay.
25
to remove
7 of procedure
in ml.
into ether.
with HaS
Gallium
zinc ia
(Eiclneutralized
for zinc activity.
is evaporated
1
The
to dryness
Pro&sdure
3
Qalliuni.
J. A. Marin,slw
Source:
c!hem.&
and, E. Eichler,
223:,(1960).
2 ml. uranyl
Target:
nitrate
u/ml. ).
solution
(approximately
2 minutes
time:
ratory
Reactor.
x-10
1 - After
850 mg.
..
,.
Irradiaticm
Step
J. Inorg. Nucl.
in o+
Ridge National
Labo-
,.
2 minute
decay period
very short-lived
isotopes,
to permit
solution
decay of
is trans-
ferred to a separator
funnel containing
(approximately
Ga carrier,
20 w.)
20 reg.) Ba aarrier
proximately
2 ml.
2 ml.
(ap-
and 6 ml.
12~
HC1.
Step
2 - Solution
with
30 sec.
ether
- “15to
rated
from aqueous
provide
Step
is contacted
(12.8 WY
phase
fission-yield
3 - Ga is back extracted
12 ml. of diisopropyl
ali@ot
Ba140
is sepa-
sampiea “to
,,
standard.)
into 10 ml. HaO after wash-
ing ether” layer witl”three
5 mi. pofiions’of
6K
HC1.
Step
4 - Solution “is made lE in HF” and then passed
Dowex-1
anion exahange
compressed
lected
Step
column
air ‘toadsorb
Me).
tirough
(with the”aid
Effluent
of
is col-
in 5 ml. co”nc. HBr.
5 - Acid mixture
evaporated
26
just to mess.
Residue
Procedure 3 (Continued)
is innnediateiy dissolved
and the Ga extracted
In 10 ml. chilled
wI*
6~ HC1
10 ml. cold diisopropyl
etier.
6 -
step
Ether
=tract
of 63 HC1.
Step
7 - Aqueous
ia washed
Ga is back
sample
twice with
extracted
5 ml. portions
into 10 ml. HzO.
18 made 0.3~ in HC1 after addition
of 10 mg. Bi and approximately
3 mg. MO scavenger
carriers.
Step
8 - Bi aad MO are precipitated
tate
are removed.
with H2S ati precipi-
Additional
MO ia”precipitated
with a-benzoinoxime.
step
9 - Filtrate
is made
slimtly
Ga in precipitated
Step
with
10 - Ga-8-hydroxyquinolate
for activity
baaic
with
6E ~oH
8-hydroxyquiholine
ia filtered’on
p“a~r
and
reagent.
disk
measurement.
&cedure
4
Gallium
Source:
Irwin J. Gruverman
Radiation
and Isotopes
Isotope:
Ga67
Target
Material:
Product:
and Paul KXuger,
~, No. 1, 21
J. Applied
(1959).
zinc
98+% G.67 pure
HNOS or HC1 solution.
combined
gallium
activities
in
Procedure 4 (Continued)
Product
Reactions:
,,
Chemical
separation
from HN40H
2-
(d,2n)
==67
Principles:
Ga is carried
cu is retained
on Fe(OH)s
in supernate.
KOH solution.
Fe
IS
K and residual
Cu
80+%
6 HOLUS
zn target,
minhum
Step
Zn67
by ion exchange.
Time Required:
1-
~a67
from strong
are separated
Step
(d,n)
solution.
precipitated
Recovery:
Zn66
approximately
of HC1.
5 g., is dissolved
Solution
20 mg. each of Fe
la diluted
(III) and cu
in a
to 100 ml.
(II) carriers
are
added.
Step
3-
PH la adjuated
ed to digest
Step
4-
Precipitate
solved
Step
5-
to 5.5 with
lmhoH:
solution
allow-
15 minutes.
ia removed
by centrifugation
in .HC1. A second precipitation
ed to inmre
separation
Precipitate
la diaaolved
Hcl: volume
is adjuated
and &hsla perfom-
from’ Cu.
in a minimam
amoumt
to 20 ml. with H~Oj
of
an ex-
teas of KOH is added.
Step
6-
Heat to boil;
fugation.
gallate
Step
7-
precipitate
Supernate,
ia separated
which
contains
by centri-
activity
aa
ion, is reserved.
Precipitate
cipitation
la dissolved
is made.
28
in HC1 and a second pre-
Procedure 4 (Contkued)
Step
B - supernateo
excess
Step
HC1 is added
9 - Solution
has been
volumes
move
are combined,
is passed
neutralized
to make
through
conditioned
wI*
solution
Cu.
3y in HC1.
a Dowex-1
3~ HC1.
of 3N HC1 are passed
K and residual
with HC1 and
column
Three
through
which
column
column.to
Ga is eluted
re-
with 0.2~
Hcl.
Step 10 - Solution
is evaporated
matter
is r&oved
peated
evaporations
to ne~
dryness:
by evaporation
organic
with HNOS.
with HC1 convert
Re-
the gallium
to the chloride.
Procedure
5
“Gallium
source:
H. J. M. Bowen,
and Isotopes
Target
&, 227
Time:
J. of Applied
Radiation
(1959).
0.3 g. tomato
Material:
Irradiation
Internat.
12 hours
seeds;
5 g. blood.
at approximately
1 x 1012
n/cm2/sec.
Time Required:
(MO + Ga) approximately
4 hours
for 8 sam-
pies.
Step
1 - Seeds are dissolved
is dissolved
in hot
drops perchloric
in hot
fuming HMOS.
fuming HNO= plus
acid.
29
Blood
a few
Procedure 5 (Continued)
Step
2 - Carriers:
10 mg. MO as ammonium
Ga as gallium
nitrate.
Holdback
molybdate;
5 mg.
carriers:
Cu,
CO, Mn, P snd Y.
Step
3 - Solution
ia evaporated
to approximately
1 ml.
Made up to 10 ml. and 6E In HC1..
Step
4 - Solution
is transferred
shaken with equal
is discarded;
step
5 - Ether
to separator
volume
ether
is waahed
layer Is extrected
Aqaeous
layers
of ether;
aqueous
twice with
twice with
are combined
funnel
end
layer
63 HC1.
5 ml. HsO.
and boiled
to rexmva
ether.
Step
6 - Aqueona
fraction
precipitated
Step
7 - Supernate
and made
1.smade
with
to four times with
Step
8 - Gallium
chemical
Yieldz
Ga) is boiled
with potash
and scavenged
as 8-hydxoxyquinolate
acetate buffer
50-70%.
to remove
HRS
three
Fe(OH)~.
is precipitated
an ammonium
is
anunonium sulfide.
(containing
alkaline
2~ in HC1 and MoS
solution
in
of pH-6.
Chief contaminant in galli%m frti-
tion identified as P32.
30
Procedure 6
Gallium
Sowce
:
man, -al.
Ridge,
W. A. Brooksbank,
G. W. Leddicotte
Cbam. Div. , oak Ridge National
Tennessee,
J. Phys.
Chern. ~,
Gallium
1 - Aluminum
target
of concentrated
concentrated
evaporated
Step
LSbOratOrY,
815
(November
Oak
1953).
in Aluminum
0.1 to 0.2 g. aluminum in quartz tubes .
TUgOt:
Step
and H. A. Mahl-
2 -
is diseolvgd
HC1.
in small
Standardized
HBr are added
Smotit
Ga carrier
and the solution
and
IB
to dryness.
Reeidue
is dissolved
tracted
three
in 6~ HC1 and solution
times with
equal
volume
is ex-
of diethyl
ether.
step
3 - Bxtracts
are combined
the gallium
of H30.
is back
and waahed
extracted
with
6q HC1 and
into an equal volume
Cu, Fe and Ba holdback
carriers
are added
to the solution.
Step
4 - Cu is removed by Has precipitation;
raved
Step
5 - After
by precipitation
filtration,
the gallium
diethyl
Step
6 - Gallim
with NaOH
solution
1s made
Fe and Ba are
and NasCOs.
6~ In HC1 end
is extracted with an equal volum
of
ether.
is back
layer is heated
extraoted
to expel
31
into Hao and the aqueous
equilibrated
ether.
-
procedure
Step
7 ‘- A few ml. of B-hydro~quinoline
in 2M acetic
quinolate
acid)
8 - Afti&
dried
with
solution
(50 g./l
are added and gallium
IS precipitated
of 6U ammonium
Step
6 (Continued)
with
dropwise
8-hydroWaddition
acetate.
filtration,
precipitate
for 15 minutes
scintillation
is washed
with HaO,
at 11O”C, weighed;
counted
detector.
Procedure
7
Aluminum
Sourae:
R. A. Rightmire,
T. P. Kohman
Internat.
J. Applied
Element:
Al” - Carrier-free
Separated
from:
D8COnt8d.natiOII
Chemical&
Radiation
@gnesium
Faator:
end IOotopea
~, 274
(1957).
A126.
(U bombarded).
>108
and Equipment:”
aa follows;
and A. J. Allen,
Polyethylene
ion exchange
aolunwe
2 - 35 cm. x 1 cm.
1 -60cm.
DO~X-1’
xlm.
(1OO-2OO megh)
ing with
Dowex-50
12~ HC1,
with
iron, then with
- coated
by waeh-
followed by H50.
- prepared
(50-100 msh)
ing thoroughly
Glaemiare
- prepared
by waeh-
6N HCl until
“free of
HaO.
with
a thin
silicone
.,
film.
32
Procedure 7 (Continued)
Freshly
distilled
H20 and freshly
prepared
NH40H were used througkmut.
Step
1 -
Dissolve
activity
from megneaiun””t&get
with
6N
.
HC1.
A.
Step
Separ ation,of
2 -
Al from Mq and Na
Add Hao until
twice
methyl
volum
Of Be+2,
Ca+2
red. indicator.
end point
is approx-tely
6N HC1 added in Step 1.
of
the amount
10 “&g..‘e~h
~d
Add NH40H
to precipitate
3 - centrifuge;
Add
SC+3 carriers
to methyl
Be(OH)~
at 50-60”C “Yor 10 minutes
Digest
Step
solution
wash precipitate””with
plus
red
and Sc(OH)g.
tid cool.
0.00IE NH.40H.
:,..
B.
step
Purification
o! A126
4 - The precipitate
xl
+ O.~
anion
5 - ~
o.~
Be2+
column
wlkh
+ O.~HSCZO~l.
is eluted
in 100 ml. of 0..l5~
and introduced
wi&
onto” a s=11
had-been’ filled to a
of 20 cm. tid washed
(0.12~HCl
Step
hs dis~olved
HrX%04
exchange
height
,.
with
500”ml.
““See Note
50 “ml. of
HSC=04), or ur&il
no
precipi”tite
of
1.
(0.”15g HC1 +
Of Be(OH)a
forms In the elute upon addition of NH’40H.
Step
6 - The Alw
is eluted
the eluate
with
is’dihtdd
50 ml. of”12~HCl,”
with
,,.,
Few
is
added.
33
and’
100 ml. Hao and 30 mg.
Procedure 7 (Continued)
Step
7-
The solution
is made
the precipitate
slightly
basic
is digested
with NH40H,
at 50-60”c
for
and washed,
and
one half ta one hour .
Step
Step
8-
9-
The precipitate
is centrifuged
the
solution
aupernatant
The precipitate
is dissolved
HC.1 and the solution
cation
exchange
a height
and washings
with
Introduced
column
discarded.
50 ml. 0.50~
onto a small
which had been
to 20 cm. and washed
filled to
thoroughly
with
Hao.
Step 10 - The
flow rate is adjusted
the column
is washed
Step 11 - Fe3+ and Alw
column
with
are eluted
volumes
to LO drops/minute
50 ml. 0.80x Hc1.
with
in a volum
is added, and the solution
step 13 - Vanadium
by heating
carrier
ing 10 mg. vf405
the above
at 70-80”c.
see Note
aoluti.on is prepared
j+3
5 ml.
12E HC1,
to one
2.
by dissolv-
and is added to
solution.
of dilute
NH40H,
and washed
with
a slight
and 151s precipitate
excess
centrifuged
with H20.
Step 15 - The precipitate
solution
equal to the above
concentrated
Step 14 - The soluti’on is made basic
and me
of four
a minimm
5M HC1.
Step 12 - Concentrated’ HNOS
half volume
and
solution
is dissolved
satuxated
is introduced
34
in 10 ml.
12N Hc1,
with HC1 gas.
The
onto a large anion-xchanger
Procedure 7 (Continued)
Step
column
Which
had been prepared
height
of 50 cm. and washing
16 - The flow rate
i~ adj u~ted
the carrier-free
volumes
M2’ la
of 12~ HC.1.
by
with
filling
to a
12~ HCI.
to 10 drops/minute,
waehed
See Note
out with
and
1.5 column
3.
NOJ?ES
(1)
The
flow rate was adjusted
(2)
Venadium
(3)
To convert
is converted
HNOS were
to it8 highe~t
to a chloride
added,
sure of A1C$9
solution,
and the solution
in a silicone-coated
done cautiously
to 8-10 drops/minute.
beaker.
because
oxidetion
200 ml. of eonc.
evaporated
The evaporation
of the significant
at elevated
state.
to 10 nil..
must be
vapor pres-=
temperatures.
Prooedure 8
Galll-
Source:
Radiation
G. M. Iddinga,
LabOratOry,
Purification:
old solution
University
Livermore,
of California,
California.
109 atoms of Ga 72 isolated
of 2.6 x 1014
foreign radionuclides
when
fr~
fissions
she-d
followd
through
liveai.
35
Lawrence
a 36-hour
no detectable
eleven
balf-
Procedure 8 (Continued)
Yield:
step
About
70%
1 - Toa6g
HC1 solutionof
125 ml. Erlenmeyer
2 -
activities
in a
flask, add 10 nq. Ga carrier
and 1 mg. Te+4 carrier.
Boil
minutes.
should be approximately
Final
20 ml.
Step
mixed
solution
solution
for 10
(Note 1)
Cool and transfer
cal, open-top,
tached
solution
separator
bmediately
to a 60 ml. cyli&rifunnel
below
(with stem de-
the stopcook).
Add 4
ml. cone. E@l to the 20 ml. of 6~ HC1 to make
solution
73 in HC1.
isopropyl
ether
and extract
by rapid stirring
stirrer
this
step
(paddle)
separation
3 - Drain
minutes.
Step
RePeat
Step
aqueous
time of
layer.
Wash organic
15 ml. of 7X HC1
for two
the Ga from the ether with approxi-
layers
approximately
for two minutes.
with
10 ml. of water
in a 40 ml. centrifuge
5 - Add 5 rng. Fe+3 carrier.
water bath
Record
rod
7~ HC1 wash.
extraction
bine water
minutes.
glass
of Zn 72 from Ga72.
15 ml. of water
the back
25”ml.
the Ga into the ether
a rotor-driven
approximately
4 - Back eX&act
mately
with
for tm
and discard
layer with
Add approximately
13”(0.U
3 minutes
Add
and comcone.
10~ Na@. mtil
in OH-).
to coagulate
36
Repeat
pH IS
Heat on boiling
Fe(OH)g
ppt.
Procedure 8 (Continued)
Cool to room temperature.
the Fe(OH)3
Step
6 - Tr~sfer
separator
funnel
previously).
7.
(identical
(The solution
adding
the formic
and extract
phase by rapid
Immediately
peat 1~ NaoH wash.
proximately
Wash
organic
layer during
9 - Combine
water
aqueous
organic
lay-
layer and re-
layer with
ap-
for ten seconds.
approximately
extracting
these washes.
the Ga with
15 ml. of
Repeat
be-
from the orSee Note 2.)
approximately
for 20 minutes.
15 ml of
Hcl back
cone.
for 20 minutes.
cone.
until
Wash organic
(Step 7 should be done quickly
ganic
extraction
Step
wash
Ga is slowly back
cone. HC1
30 ml. of 0.40~ TTA
layer.
drain
layer w%th
extract
at pH 3.3-3.6 by
15 ml. of lx NaoEi for ten
cause
8 - Back
formic
for 15minutes.
15 ml. of,water
1~ HC1 twice.
Step
Add
aqueous
approximately
seconds.
of cone.
the Ga into the TTA-benzene
stirring
and discard
with
the pH is approxhnately
is buffered
acid.)
the one used
amc$unt (4 or 5 drops)
this,amount
acid.
er
with
Add a measured
Then add twice
7 - Drain
to a new 60 ml. cylindrical
formic acid until
in benzene
Step
and discard
precipitate.
the supernate
of cone.
centrifuge
HC1 solutions
the solution
(add approximately
and dilute
is approximately
21 ml. of water
“37’
it with
7g HC1
to 30 ml. of
Procedure 8 (Continued)
cone.
HC1).
Transfer
ml. cylindrical,
open-top,
(with stem detached
funne1
separator
immediately
the stop-
below
Add approximately 30 ml. of isopropyl
cock) .
ether
to a 125
7g HC1 solution
and extract the Ga into the ether by rapid
stirring for two minutes.
step 10 - Drain and discard aqueous layer.
Wash organic
layer with approximately 15 ml. of 7~ HC1 for two
ndnutes.
Repeat 7~ HC1 wash.
Step 11 - Back extract the G“a from the ether with approxi-
mately 10 ml. of water for two minutes.
Repeat
the back extraction with approximately 10 ml. of
water.
Step 12 - Combine
water
fuge cone.
rated
Add approximately
solution
the solution
- Filter
filter paper
Step
14 - Powder
m@m
Heat
Ga(OH)g
until
in boil-
for ten minutes.
No. 42 filter
2 per cent NHAN09.
a poreclain
crucfile
for
at 9OO-1OOO”C.
the Gazo3
“hat”.
ing plate.and
and/or
in
with
dropwise
pH-6 .
with Whatman
Wash precipitate
one hour
0.5 ml. of a satu-
Add NH40H
to precipitate
out Ga(oH)3
paper.
Ignite
of NH-.
is approxtitely
ing water bath
Step13
of Ga in a 40 ml. centri-
solutions
and transfer
Weigh.
count
it to a taxed
alu-
Mount hat on “aluminum countthe 14.3-hour
ganuna counter.
38
Ga72
in a beta
Procedure 8 (Continued)
(1)
Boiling
any Te +6 to Te’4 and ensures
in 6~ HC1 reduces
complete
exchange
between
‘re carrier
and radioactive
Te.
(2) The ~
NaOH washes
layer,
with
leaving
the “free” TTA away
the Ga-TTA
chelate.
1~ HC1, the equilibrium
tends
to leave the organic
from tie benzene
In subsequent
Is shifted
layer.
washes
so that the Ga
However,
‘in low
‘+3, Al
acid (~ HC1) the rate is ‘slow (similex to “Fe
such as Zr, NP+4 , rare earths,
and Bej.
Elements
Th, etc.,
are rapidly
when
there’is
back
essentially
extracted
Pa,
into the N_ HC1
no “frea” TT.A in the
benzene.
Procedure
9
,,
,.
Gallium
Harrison
Source:
347
Brown
andEdward
Gcildberg,
science
~,
(1949).
Target:
Unknown
- 0.3 to 0.5 g. iron meteorite.
- 10 mg. gallium
,.
Standard
Irradiation
- approximately
8-hydro~quinolate.
30 minutes
at 1012
n/cm2/sec.
A.
Step
chemical Processing of Meteorite Unknown
1 - Sample
is dissolved
50 ml. beaker.
in h’otconceritrated
4-5 mg. Ga+3 carrier
39
IiCl in
added.
-
Procedure 9 (Continued)
2 - Adjust
Step
solution
acid.
Extract
saturated
with
to 5.5 to 6.5~ in hydrochloric
gallium
ether.
with
equal volume
Strip galll~
of HC1
from ether phase
HzO.
step
3 - Repeat Step 2.
Step
4 - Precipitate
droxide
ether from aqueous phase.
ion by addition of NaoH (hy-
ferric
concentration
of l-2~).
centrifuge,
and discard
aeroeol,
Acidify
Evaporate
supernate
to pH-1
Add
one drop of
precipitate.
and heat
to 60-70°C.
5 - Add 5 ml. of a 1 per cent acetic acid solution
Step
S-hydroxyquinoline.
wise)
Add
to completely
3M ammonium
precipitate
acetate
gallium
of
(drop-
8-hydroxy-
quinolate.
Step
wash precipitate
6 - Filter;
by ether.
termine
B.
Processing
step
Dry sample
with hot water
15 minutes
followed
.
at llO°C and de-
yield.
of Gallium
1 - Dissolve
Standard
10 mg. quantity
nolate,
which
was
ditions
as the meteorite
of gallium 8-hydroxyqui-
irradiated
under
sample,
identical
con-
in hot concentra-
ted HC1.
step
2 - Dilute
to 50 ml.
quantity
Take 0.S ml. aliquot;
of gallium
precipitate
carrier
as above.
40
add same
aE for the unknown
and
Procedure
10
Aluminum
Source:
W. D. Ehmann
mochimica
Materials:
Acts 14,
and T. P. XOhman,
340
Geochtica
et Co13-
(1958).
A.
chemicals
- reagent
B.
Filtering
- analytical
c.
IOn Exchange
Resins
1.
X-10,
Dowex-1,
grade
gradeta (Wl&tman)
100-200
mesh anion
exchange.
X-8, 50-100 mesh cation
Dowsx-50,
2.
exchange.
A.
Procedure
for Iron Meteorites
Iron meteorite
distilled
step
E_ple--100
1 - Sample
ia dlaeolved
beakers
until
in consecutive
each portion
complete
2 - 25 ml. concentrated
tions to oxidize
evaporated
3 - solution
HNOa
excess
filtered
200 ml. portions
in separate
im achieved.
is added to ccmbined
.
all Fe2+ to Fe-.
is adjusted
(solution
etirred
dissolution
to near dryness
of HC1 to rem&e
Step
with
HzO and acetone.
of aqua regia,
step
Washed
to 150 g.
with
solution
soluis
500 ml. portions
HUOg.
to one liter with
[whatman-50
paper]
9~ HC1
and residues
discarded).
Step
4 - Accurately
known
quantities
41
of tlie following
car-
Procedure 10 (Continued)
riera
A1+3-,20 rng.; Be 2+-13.9
are added:
ca2+-20
mg.
Iron is removed by extraction
,.
9~ HC1 saturated
Step
isopropyl
ether.
the aqueous
phase
proceeds
5 - The aqueous
phase
is adjusted
volume
Do-x-l
reg.;
into
Proceaeing
of
as follows:
.,
to 10H in HC1
(total
approximately
750 ml. ) and passed through
..
Alw,
which is not adsorbed in
column.
the column
is retained
Ca+2r Be2+
and others.
in the elute
Column
ml.” of 10~ HC1 end the washings
a
along with Ni2+,
is washed
with
combined
500
with the
main elute.
Step
6 - The. elute
from Step.5
ml. and A1(OH)9
NH40H
and Be(oH)a
(PH approximately
ered on Millipore
of 5% NH@l
hydroxides
cipltated
Step
7“- A1(OH)9
is reduced. in volfi
n
adjusted
are precipitated
Hydroxide
7).
paper
end washed
and filtered
with
are filtwith
to approxi.inately pH 7.
are dissolved
to 300
25 ml.
The
in diltite Hc1 and repre-
twice.
and Be(oH)a precipitates” are tran’eferred
to a 250 ml. beaker, 10-20 rng. Fe3+ carrier is
“added plus
filter
25 ml. of 8~ NaoH.
insoluble
precipitated
step
hydroxides
on fritted
a - Reprecipitate
after diluting
Al(OH)g
to boiling
scavenged
by Fe(OH)=
6~ HC1
to 250 ml. wi~”HzO.
in dilute
42
and
glaarn.
and Be(OH)awith
filtrate
solve precipitate
Heat
Dis-
HC1 “and reprecipitate
Procedure 10 (Cont@ued)
twicq wi’~ NH40H
Step
9 - Dissolve
6~ HC1.
l.l&HCl
to remove
Na+.
A1(OH)S
and Be(QH)=
DllUte
to” 50 ml. wi&
With
H40 and make to
step .10 - Pass, solution. through, 25 ml. resin
column
(10 in.
flow rate of approximately
with
6-7 resin volumes
in column
of
‘
HC1.
6~
ion exchange
volume
in minti
volume
Dowex-5Q
x 1/2 in. dismeter):qt
1 ml./min.
of l.~_ HC1.
EIUte Be2+”
Alw
held
iS
12 to 15 resin
but will elute with
vol-
umes of l.U_ HC1.
100 ml. of 3M HC1.
step 11 - Elute A13+’with
step
12 - Reduce
volume
of A13+
on hot plate.
cool on ice bath
5 ml. of 12~ HC1.
tion
Bubble
for 5 minutes;
tinue gassing
cating
until
saturation
on standing
contalntng
solution
to l~°C and add
dry ,x1 gas through
add 10 ml. ethyl
solution
by HC1.
for extended
to 5 ml.
ether
and con-
layers combine
AICl~-6Ha0
period
solu-
indi-
precipitates
In ice bath.
Filter precipitate
by suction
on fritted
and wash with cold
1:1 12~ Hcl-ether
glass
solution
disc
satu-
rated with HC1.
Step
13 - Dissolve
twice
A1C19.6H20
and finally
8tep 14 - Precipitate
end-point.
filter
h
in 5 ml. HeO; reprecipitate
dissolve
in distilled
Hao.
Al(~)s
with NH40H
at methyl-red
Collect
precipitate
on Millipore
Btichner funnel.
43
HA
“Procedure10 (Continued)
Step 15 - Ignite
B.
to A1z03
at 1000°C
in”platiti~” dish.
Procedure
for Silicate Materials
.
Procedure is similar to that for meteorite sample
except” for dissolution
of sampie,
and sizes of ion exchange
amounts of reagents used
columns .
,..
,:.,
..
,;.
,,
,)”,
>-
,..
44
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USMC OffI.o d Technicallnk,m@Ion EXMNI.., Ode RI+,
48
T,nn-