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!NationalAcademy vofSciences .
National Research Council
NUCLEAR SCIENCE SERIES
I The Radiochemistry
I
of Sodium
COMMITTEEON NUCLEAR SCIENCE
L. F. CURTISS, Chairman ROBLEY D. EVANS, ViceChairman
National Bureau of standards Massachusetts Instituteof Technology
J. A. DeJUREN, Secretary
Westinghouse Electric Corporation
C. J. BORKOWSKI J. W. fRVINE, JR.
Oak Ridge National Laboratory Massachusetts Institutenf Technology
ROBERT G. COCHRAN
Texas Agricultural and Mechanical
College
SAMUEL EPSTEIN
California Instituteof Technology
U. FANO
National Bureau of Standards
HERBERT GOLDSTEIN
Nuclear DevelopmentCorporation of
America
E. D. KLEMA
Northwestern University
W. WAYNE MEDiKE
University of Michigan
J. J. NICKSON
Memorial Hospital, New York
ROBERT L. PLATZMAN
Laborstnire de Chimie Phyeique
D. M. VAN PATTER
Bartol Research Foundation
LIAISON MEMBERS
PAUL C. AEBERSOLD CHARLES K. REED
Atomic Energy Commission U. S. Air Force
J. HOWARD McMILLEN WILLIAM E. WRIGHT
National Science Foundation Office of Naval Research
SUBCOMMITTEE ON RALNOCHEMISTRY
W. WAYNE MEINKE, Chairman EARL HYDE
University of Michigan University of California (Berkeley)
NATHAN BALLOU JULIAN NIELSEN
Naval Radiological Defense Laboratory Hanford Laboratories
GREGORY R. CHOPPIN G. DAVID O’KELLEY
Florida State Universi@ Oak Ridge National Laboratory
GEORGE A. COWAN ELLIS P. STEINBERG
Los AlamOs Scientific Laboratory Argonne National Laboratory
.
ARTHUR W. FAIRHALL PETER C. STEVENSON
University of Washington University of California (LivermOre)
JEROME HuDIS DUANE N. sUNDERMAN
BrookhavenNational Laboratory Battelle Memorial Institute
CCWSULTANTS
HERBERT M. CLARK JOHN W. WINCHESTER
Rensselaer Polytechnic Institute Massachusetts fnstituteof Technology
The Radiochemistry of sodium
w. T. MjLLINS AND G. W. LEDDICOTTE
t2ah Ridge .Natt”ond Lahorator>
Oak Ridge. Tennessee
Imueme Date: Much 1962
MS ALAams
SCIENTIFIC M.WFUTORY
Subcommittee on Radkhemi*ry
National Academy of Sciences —National Research Council
Prmti in WA. PriceS0.60. A=eikhlefromrhe Officed Tedmlmi
Services, DepunnentofComuiema W.WMWDJU W D. c.
FOREWORD
The Subcommittee on Radiochemistry Is one of a number of
mbcommltteea working under the Committee on Nuclear Science
within the National Academy of Sciences - National Research
council . Its member6 represent government, induatrlal, and
university laboratories In the areas of nuclear chemistry and
analytical chemistry-
The Subcommittee has concerned Itself w%th those areas of
nuclear science which tivolve the ohemlst, Buch as the collec-
&ion and distribution of radiochemlcal procedures, the e~tab-
llshment of speclflcatlons for radlochemically pure reagentB,
avallabilit$ of cyclotron time for service Irradiations, the
plaoe of radiochemlstry i.n the undergraduate college program,
etc.
This series of monographs has grown out of the need for
up-to-date compilations of radlochemical information end pro-
cedure.B. The Subcommittee has endeavored to Present a aeriea
which will be of maxim~ uae to the working scientist and
which contains the. latest available information. Each mono-
graph collects in one volume the perttient information required
for radiochemlcal work with an Individual element or a group of
olosely related ,elementa.
An expert in the radloohemistry of the particular element
has written the monograph, following a standard format developed
by the Subcommittee. The Atomic ’Ehergy Connnission has sponsored
the printtig of the series.
The Subcommittee is confident these publications will be
useful not only to the radiochemist but also to the reeearch
worker h other fields such as physics, biochemistry or medicine
who wiehes to use radlochemical techniques to solve a specific
problem.
W. Wayne Meinke, Chairman
Subcommittee on Radlochemistry
. . .
111
INTRODUCTION
iv
I.
II.
III.
Iv.
v.
VI.
VII.
v.
——-.——. -——
Geneti Reference8 on the Inorganic and Analytical
Chemistry ofscriium. m.... . . . . . . . . . . . . .
Radioactive Nuclides of Sodium . . . . . . . . . . . . .
The Chemistry of SodiuIUand Its Application in
AnalyEls M?thods for Stable Sodium or Its Radionuclides.
A. The Geneti Chemistry of Sodium. . . . . . . . . . .
1. Metalllcsmthun.. . . . . . . . . . . . . . . .
2. The Chemical Gxq0und60fS&um . . . .. . . .
a. Sodium Hy&ide, NaR. .,. . . . . . . . . .
b. !l!hetiid es ofsodiu m.... . . . . . . . .
Ek=Mum Hydroxide, NaOH, . . . . . . . . . .
:: !CheNitrogen Conrpounda, . . . . . . . . . .
e. The Sulfide. Sulfate. and SuMite Camound.e.
f. The Halogen”Compouu&. . ,
The Phosphorus Cknnpounde.
:: The Carbonate Compmnda. .
i. Sodium cyanide . . . . . .
J. Other Sodium compounds . .
B. The Analytical Chemistry of .%dium
1. Sepsxationsby Rreclpitatlon .
2. Sepamtione by Electrolysis. .
Solvent Exkaction S~thru3
z: ChrcauLtoPphy Separations . .
a. Witi Organic Adaorbents. .
b. With Ion Exchange Resine .
c. By Papr Chromatography. .
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Dissolution of Samples Containing Sodium . . . . . . . .
S#ety-ctices . . . . . . . . . . . . . . . . . . . .
tiunting Tecbnlques for t~ Re.dioactiveSC-Mum Isotopes.
RsiMochemLcal R’oceduns for the Sodium Radlonuclides. .
References . . . . . . . . . . . . . . . . . . . . . .
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39
v
The Radiochemistry of Sodium
W. T. MULLINS AND G. W. LEDDICOTTE
Oak Ridge National Laboratory *
: Oak Ridge, Tennessee
I. GENERAL REFERENCES ON THE INORGANIC AND ANALYTICAL CH@@IWY
OF SODIUM
Remy, H,, Treatise on Inorganlc chemistq, Vol~ I, Eleevier,
AmeterdeJn(1955).
Kleinberg, J., Argerelnger,W. J., Jr., and Griswold, E., Ihorganic
chemistry, Heath, I!aston(1~0) .
Hillebrand,“W.F., Lundel.1,G. E. F., Bright, H. A., and Hoffmm,
J. L., Applied InorganIc AnalysiB, John Wiley and Sorm, New York,
1958.
Wilson, C. L., and Wilson, D. W., ComprehensiveAnalytical Chemistry,
Elsevier, Amsterdam, 1959.
Sienko, M. J., and Plane, R. A., Chemistv, McGraw-HilJ, New York,
1957.
Chariot, G., and Bezier, D., Quantitative horganic fqalysi~> John
Wiley and Some, Ww!iork, 1957.
Sidgwlck, N. V., The CinemicalElements and Their Corapounda,
Ihiveraity Press, Oxford, 1951.
Hutchinaon, E., Chemistry - The Elements and Theti Reactions, Saunders,
Philadelphia, 1959.
Sneed, M. C, and Maynard, J. C., General College
44.
Chemlatry, Van Nostrand,
New York, 19
Sneed, M. C., and Brasted, R. C., Comprehensive Inorganic Chel?dstry,
Volwne 6, Whe Mkall Metals,” Van Nostrand, NewYork, 1957.
LatNner, W. M., and Hildebrand, J. H., Reference Bcok of Inorganic
chemistry,MacMillan”New York; 1940.
*Operated for U. S. Atomic Energy Comisslon by Union Carbide Corpmation
1
II. TEE RADIOACTIVE NUCLIDES OF SODIUM
The radionuclidesof sodium that are of imberest in the ra.dlochemdstry
of sodium are given b Table I. This Table hae been completed from irfor-
(1)
m3tion appearing In reports by Strominger, et al, and by Hughes and
Eku’veyw
Half-
Llfe
0.3s5 s
23 6
2.6 Y.
15 h
as
TABLE I
TIIERADIOACTIVE NUCLIDES OF SODIUM
Mode of Energy of
-
Rdiatlon, Mew
P+ P+ 3.5
P+ p+ 2.5
P-
p-
@+ 0.542
@- 1.39, 4.14
Y 1.38, 2.76
P- 3.7, ‘.7
Produced By
Ne-p-m, W-y- 3U
20
-p-y, N -p-n, Ne-d~n
tg-p-a, & -p-a
F-~m, He-d-n, Ne2~-p-y
Na-n-2n, *-d-a
Na-d-p, Na-n-y, Mg-d-a
Mg-n-p, Mg-y-p, Al-n-a
Al-d-pa, Al-y-@p, Al-p-2-n
3i-7-2p
Ms-7-P, ~-n-p
m-y-2p
III. THE ~ OF SODllM AND ITS APPLICNCION IN AK41.YSISMETHODS
FQR 91!4BLESOD~ OR ITS RADIONUCLIEE9
Redioch&ulcal analysis =thode usually follow the Ideas and techniques
established in conventionalmethcde, such ae precipitation, solvent ex’crac-
tion, chrcmmtogIaphy,and electrolyels. Since these methods are dependent
upon chemical reactions to bring them to completion, the general bfonnatlon
presented below on the formation of acdlum compunds attempts to relate
these more conventionalmethods to the radlochemisiaymethods used in
ana~~ a ~~ctive matefid for the sciliumradionuctides.
A. The Geneml Chemistry of ‘odium
Sadlum composes about 2.83$ of the earth’s cruet and occurs”pfincisly
in the form of scdium chloride. Other natural compounds of Eodium include
the titrate, the sulfate, the csxbonate, the bicarbonate, and the tetraborate
compouude. sodium also occurs as the silicate In ingeous rocks. Most of the
~-~ c~ ~ found in soils, nters, and in the bodies of plsmta
2
sad aDlnlsls. Sodiummetal Is chiefly
flrBt preparing the chloride and then
BOdiUI!J carbonate.
produced fram these compounds by
electrolytlcalJyfusing it nlth
1. MetalXc Sodium
Sodium metal is a soft, silver-white met-alhaving a demi~ of O.~
and a melting @nt of 97.5°. It ~shes quickly in air and must be
kept under a Ilquid such as kerosene. It will burn h air with a bright
yellow flame, and it reacta violently with water. It will unite directly
with the halogens, sulfur, selenium,,and tellurlum. Sodium forms an
amalgam with mercu# to become a very active reduc~ agent. Sodium also
alloys with lead, tin, and anthony, but it will not alloy with iron.
2. The Chemical Compunde of sodium
The only oxidation state of sodium is +1. Its reactions with carbon
dioxide, hydrogen, Wgen, nitrogen, sdfur, W the halogens are similar
to those for the other alkali metals, 1.e., llthium, potassium, rubidium,
and cesiwn. Its violent reactions with water and aqueous solutions can be
moderated by using an ~, i.e., a solution of sodium in mercury.
Sodium also forms etrong salts with au of the common acids.
Table II shows the relative solubil.ityof may of the sdlum compmnda
in %mter and other reagents. The folloulng information gene- describes
the reactions of sodium with other el-nta.
a. The Hydrogen COlnpOund. S9dlUm hydxide, NaH, cau be fozmed by
heating sodium and hydrogen directly. It has a melting petit of 800°. ‘l?ne
-de reacts with w=ter to produce hydrogen gas.
b. The Oxide Compounds. Two oxide compounds are fomed by sodium
in ite reactions with ~gen: no?xml oxide, Nh20, and the peroxide, Na O2 2“
Sodium rcmcmide, Na20, is formed by heating either sodium hydroxide, or
sodium nltmte with excess sdium metal. It can also be formed by heating
a mixtme of sodium azide, NaN
3’
and mdlum nit=te at 280°. Na20 is a
colorless compound that combties with wwter to form NaOH.
Sdiuln peroxide,
air or oxygen. Na202
is added to a ndxture
‘a202‘ ie formed by burning scdium in ~ excess of
is a pale yellow solid that m&ts at h&lO. If it
of ice and water; sodium peroxide hydrate, Na202s8E20
3
is produced. When Ha202 is heated, oxygen la given off and carbon dioxide
Blowly decompose~ it to form sodium carboriateand to evolve oxygen. At
0° C, sodium peroxide reacts with elcohol to produce sodium hydrogen
peroxide, iiaETl
2“ Sodium pero~de will react with water, ~th some violence,
to produce sodium hydroxide, oxygen, aud hydrogen perotide.
~2°2’ either
in aqueous solution, or as the fused peroxide, is a powerful oxidizing agent.
c. sodium H@-o tide. !13J0general processes, i.e., the action Of
calcium hydroxide on sodium carbonate and an electrolysismethod uelng
sodium -Igam and brine, are used to prcduce eodlum hytkoxide, NaOE.
Sodium hydroxide is a colorless andwax-liks solid. It melts at 319° and
boils at about 1390°. NaOE dissolvee in water with the evolution of heat
“tomeld a strong basic solution that can be used as a precipitant for
sweral of the chemical elements.
d. tie Nitrogen CompundO. Sodium nitfide, Na3N, a salt of hydrazoic acid,
‘3”
ean be fommd by react- sodium and nitrogen in an electric discharge
tube. Sdium azide, NaN3, can also be fcn%ed by pas@g nitrous oxiti, E20, over
sdamide, N-, .ati~o. NaN3 decomposes when gently heated in vacuo to
give mdlum rdtride and nitrogen gas. The eodium nitride cmpounde are
rapidly attacked by water, forming sodium hydroxide and emmonia in the
reaction.
Sodium nitrate, NzN03, is obtained by the action of HIW3 on sodium
metal, sodlwn hydroxide, or sodium carbonate. NaNo3 is hygrcmcopic and
diseolves more rapidly in hot water than cold. It is a@drous, and it
will melt at 380° and be decomposed. When heated above @o, NaN03 will
lose oxygen and form sodium oltrite, Ne.l!122.sodium nitrite is prcduced
as very Emu, hygroscoQic crystals. NaN32 is a st~ng electrolyte, and
it will nelt upon heating to fomn a yellow liquld which decomposes at
~er tel!lpemtures.lblf02will hydrolyze to nitrous acid when boiled
ulth -*r.
e. The Sulfide, Sulfate, and Sulfil% . Sdiura till react
~1~-*’ ‘a2s2.
with a meltingpoint
to form either sodium monosulfide, Na2S, or scdlum
Sodium nmnosuJfide is a tiless crywklline solld
of UE!O”. Nn2S is hygmacopic, and it reacts readily
4
mid.
Zmbltal
hlublainmludml
SOlllblo inm; vow awiltlyMdJM.0in
&lcObl
Tnble II is continuedm tie follmvlngpage.
~
Sdnblm
SOlubln
Selmla
&lubl.a
Wlmlm
mlubl.s
alublm
Sdm10
Vmg Mlnbla
alnbu
with water to form a strongly aWaline solution.
irlaolublmin
m.ublninnlealml
allbl.ninnldnl
Sodium sulfide solutions
are unstible and till break down to form polyeulfides, thiosulfates, and
aulJ?ates. Sodium hydrogen sulfide, NaES, can be fo?.medby saturating a
sodium hydroxide solution with !&.
Sodium sulfates can occur in nature. However, Bodium hydrogen 13UM?ate,
NaISOk, iS produced by heating NaCl with an exceae of H2S0h at tempe=tures
lower than 150°. If NBHSOL is heated to about ho, it ia converted to
normal sodium sulfate, Na2S04, which is readily soluble in wster. sodium
tblo.mlfate is prepared by boiling sodium sulfite, Na SO~ ~, in the presence
of Eulfur. Sodium thiosulfate, as Na2S203”V20, is used principally in
photographic film processing. Here, tileexcess silver bromide, which remains
6
in photographic film after developing; dimaolvee very readily in the thio-
suli’ate to form a soluble complex. Soditi thiostiate 16 also used as a
tltmt for the determinationof iodine.
E031uluhydrogen sulfite, or mdiwn blsdflte, NzHS03, is formed by
satumting a solution of mdlum carbonate or mdlwn hydrcrdde with sulfur
dioxide. Normal scdium suJflte, Na2S03, is formed by treating the eolu-
tion with an additional amount of soditi carbonate~ The sulfite solutions
are.alkaltie and are god reducing agents. BoththeHso-andso--iona
3 3
are retily OXidlZed tO S04-- ions by atmmphetic oxygen or oxygen-con-
tairdng Cmlpounde.
f. The Halogen Ccmpunda. The sodium halide c
~, i.e., stim
—.
chloride, HaCl; ~ Hal?;~ NaHr; and sodium
iodide, NaI, may be prepared either by a direct union of the elemnts or
by the reaction of a halogen acid u~n sodium hydroxide or sodium carbonate.
AU of the sdium halides are strong salts and are completely ionized. They
are readily soluble in water at ma tempszatum.
Sodium salts of the oxygen acids of the halogens include sodium chlorate,
Eodlum hypoCblofite, sodium percblorat-e,SOdiUM bromte, and saiium iodate.
Sodium chlorate, liaC103,is prepared by pasBing chlorine -O into hot concen-
tmted sodium hydmxlde.
more solub~e in hot water
will decoiqose on heating
ding bromate, NaBrQ3, and
NzC103 is a colorless crystalline c~und that ie
than in cold. It is a etrong otidizing agent and
to form free chlorine and oxygen. The correspm-
the iodate, lk.10~, are PmPared in a simllm manner
and ham Bid+ properties 8.9HaCIO
3“
Sdlum percilomte, NaCIOk, is formed by the tic’ oxidation of NaC103.
It is a colorless compound and a etrong oxidiz~ agent. Sodium hypocblorite,
NaCIO, is produced by ~sing chlorine Into a cold, dilute solution of
sodium hydroxide. It is eaflilyreduced to chloride Ions and oxygen.
s. The Phosphorus Compounds. Three classes of sodium phosphate
c~cumis can be ~re~red by adding theroetical amouuts of phoe~hofic
acid, H POk,
3
to sodium hydroxide: monosodium dibydrogen phosphate,
~ ~, disodium monohydrogNaH PO en phosphate, Na2~4, and trisodium phosphate,
~a3m4 “ NaH#h IS acidic in aqueous solutions. Na2~k IS only sll@ly
7
alkallne wkile Na3FOb Is stronglyalkaline h aqueom solutions.
When sodiur W@rogen phosphate, NaH2POk, is heated, a series of
EOWJJJJmetaphofiphatecompounds are formed. They appear to be all @.y-
meric and are representedby the eqpirical formula (IkP03)n. Calcium
and magnesium ions can chelate ulth these palyphosphates. If BCdiWIImono-
-Gn phospha~, ~~~k, 16 dehydratedby heating, sodium pyruph~sphate,
17a4?207,is formed. O can be hydrolyzed in an aqueous 6olution to
‘4P2 ~
fom ~k= ions. If N.aH2POkand Na2HF0h -aremixed and heated to @O”, a
more complex phosphate, sodium triphosphate,Na P O , 1s formed.531.O ‘93°10
in solution IS S1OWIY hydrolyzed to H#04- and HK)4-- ions.
h. The C=mbotite Ccm@ounds. Two salts, sdium carbonate, NaeC03, and
.96diumhydrogen carbonate, NaHC03, are ,formedby the action of carbon dioxide
upon .90dlumhydroxide. NaHCOk crystals are redily fonued by pas13ingC02
into concentratedNaOH and they may be filtered off and dried.
‘a2c03 c-
be obtained by heating NaHC03 at temperatures above 200°.
‘a2w3 ‘U ‘e-
comlmse at t-=mpentures above 800°. The C-n -ted fO~ Of this 8alt
18 the decahydrate,Na2C03-10~O.. Holutions of Na2C03 and &HC03 are alka-
line becau8e.of the basic action of the CO ‘-
3
ioti and the slight hydrolysis
of the HCO3- ions.
i. sOdmJIIlcyalMde. NaCN, scdlum cyml.de, 18 produced by matting
dry ammonia with a molten 8odium-charcoal mixbure. It can also be
ptiuced by ‘fusing calcium cyanamide and carbon with scdium carbona~
or 8Cd1UIUchloride or ~ heating sodium carbonate, coal, and.rdtrogen
with iron as a catalyst. NaCN 18 a source of --c acid. Hodium
tmocyana te, NaSCN, can be produc@ by reacting.NaCNeither with 8uMur,
ammnlum, @.yeuEide, or sodium thlosulfate.
~.
Other Sodium Compounds. Sodium penmmgana te, Na#nOk, can be
pre~ by reacting ~se diofide with 8odium hydroxide. It ts
leas pure than potissium pemangan.9te, KpOk, and 18 very hYW8coPic.
The heating of sodium hydroxide and chromium tide in air produces
80diUIllchromate, Na2Cr04. The chrmnate salt can be efizacted from a
heated titure by a water leach. When the solution 18 heated with acid
and then waporated, ~ lia2Cr207.-O, till cry8ta3Jise
8
out of the eolution. When Na2Cr207 16 heated, It first melts and then
decompoaea into Na2C@Jk, Cr203, and f-e oxygen.
When asolution containing scdium Ions Is heated with a potasaium
salt of antimonyz a slightly soluble salt, sodium orthoantinmnate,
Na Sb(OH)6 18 prcdu’cd. Sc&um fluosilicate,Na2SU?6, Is formed in the
action of fluosiiicic acid, H2SU?~, upon a eolution of BOdium hydroxide. It
la also Insoluble in water. The aild$tionof a lirge volume of a saturated
solutlon of ua.nyl zinc acetate to a small volume containing scdlum Ions
i-esultsin the fo~tion of the ttiple acetate compound, sodium zinc
~C~te, NaC H O .5(C H O ) “~ (C H O ) 06~o, results. ThiS232 2322 22322
Compound Id a Mght.ysUou.:cry’pWline solld that is sldghtly soluble
in water.
If a solution of borax is treated with ~020rltsOHand~02, a
precipitate of Eoalllmperoxybo-te, NeW2.~0”~02. It deccsnpees very
slowly In Vat%r. It Is an active oxidizing agent. Sodium tatraborate,
~@7m10~0, -be *-M frcm natural sources h the form of ptisme.
If it Is heatedvlth scdlum~de, it foxms scdium~tibomte~ NaE02.~0.
Borexis asaltofaweakacid. It canbe hydrolyzed and its aqueous solution
glvee analkallm soluti&l.
Hum ~ de, C6H50Na, 1s fonued in the reaction of sbdium hyhmxlde
and cartdic acid”. Mauy otheror~c compoud
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