DISTRIBUTION STUDIES OF RARE EARTH
THtOCYANATES

Thai: for flu- Dogm a? Pin D.
MicH‘IGAN STATE UNIVERSITY
Rober‘r Waiter Barry
1956

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M.

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LIBRARY

Michigan State
University

 

DISTRIBUTIOI STUDIES OF KAI! IAIIB THIOCYAIAIES

'1
ROIIIJ’IILIII.IIII!

A. Ill!!!

Cull-tn“ to the School for Ahmad Grab“. India
0! the Inchigan Outta University of Agriculture
and Applied Sctancc
tn partial faltllhnanr at tho roguiruulntr
for ch: irate. of

30010! 0? PHILOSOPRI

Dcptrtnnnt of Chant-try
1956

13mm

the author eiehee to expreee hie eincere epprecietioe for
the guidance end advice of lreteeeor L. L. Quill. under vhnee
direction thie research eee conducted. end to Dr. c. I. lrubeker,

Jr., who geve Inn, valuable regaeetioee during the coeree of

thie work.

VITA

the ecthcr. Ichert Helter Berry, wee horn on October 27. l928,
in Atlente, Georgie. lie received hie ele-entery end eecondery
educetice fro. the public echoole of Atlente. In 1950. he wee
gredueted with high honor fro- the Claeoe Mricnlturel College

1with the degree a! Iechelcr of Science in Cheeietry.

In leptenher of 1950, he entered the School for Greduete
ltcdiee et lichigen Stete College, end wee e etcdent there until
June of 1951, then he vee celled to ective duty ee e eeccnd
lieuteeent in the Chnicel Corpe of the United Stetee Any. While
in the erey, the ecthor eerred ee e reeeerch phyeicel chniet et
the Chuicel Cotpe Cheeicel end ledielogicel Lehoretoriee, Any
Che-icel Center, hrylend. upon hie releeee frce ective duty,

he returned to liichigen dtete Univereity.

t. Berry ie e neuter cf the hericen Che-icel lociety,
the flociety of line Xi, end lie-e Pi dine.

I.
II.
III.

IV.

A.
I.

C.

D.

G.

flit! OI'OOIIIIII

Introduction ..---.-.----.-..--..-.-..-.-..-...-.-
lietoricel ...--.....----........--..-.._-...--_,,
Theoretieel ---------------¢----‘-------—-.--.--..
lx’etilentel .-...--.---....-....-.--.-..---....-.

Verity of here lerthe cue u-o-n-«u-n-un-

hare Berth thiocyenetee ------ ------ -.- ------ ---
1. Heady-ice thiocyeeete u---«---.-.-.-.........
I. Lutheran 'l'hiocyenete ~--—---~-----..---.--...
3- heeeodyeiu- Thiocyenete nun-«u—uunu.
lo. B-erie- Ihiocyeeete .-.......----...-...--.....

Extrection of here Berth thiocyenetce by
Tri."buty1 Mlpht. ‘- ..... o-..---..¢---ooaooo

l. Ixtrection of leodyeiuI.Ihiccyenete -----...-.
2. Ixtrectioe of Lenthnnuu Thiocyenete ~---------
3. ktrection of. Preceodyeine 'l'hiocyenete ...---.-
4. threction of seleriun.Thiocyenete ~~---------

5. Ixtrection of. Preeeody-iu- end leodynimn in
the Presence of one Another --- ............. --

Ceriu- in the preeence ct 'l'hiocyenete -- ------- «-

Verietione in the Aheorption Spectre of the
here Ierthe in rri-n—hutyl Phoephete Iolutione -

the Effect of e Snell mount of Iron en the
Dietrihction of leodynim rhiocyanete -----.-.--

The Extraction of Leathenue ‘rhiocyenete et

350 c . ....-..------..-.---.-O-..-..-..---------

12
l7
17
21
ll
2‘
26
17

27
28
35
32
52

55
58

59

71

72

V. Diecueeion - ----------------- - ..... - ........... --.. 73

A. Effect of Thiocyennte Ion Conccntretion on the
hietrihution Coefficient e! the here lerthe ---- 74

3. Dependence of the Dietrihntioe of here lerth
Ilhiocyenete on the “acne here lerth
“nutr.t1a .0.n.-.coo-.oooaoocuococconocoooa- 78

c. Dependence of the tetrection of here lerth
thiocyenetee on the Acidity e! the Menace

M. Dunn-ooocoonuooooaoooaoooooncceuoooouoaeeeoa- 82

D. Verietioe of the Dietrihctioe Coefficient with
.‘t. “rth .b:‘1 0’.‘ “.---..-0.--...DOOCC-C--- as

I. leectrel Chengee in heady-ice thiocyenete in
fri-e-hutyl l‘hoephete Solution ----------«----- 88

"e M Odqocuc-oocnoundo-o‘evoooouuoee-ocoo-e -u---.. 90
'II. '1blio‘f.’hy ;-.n.‘-Q--.-.0...couch-CuoouaaCC-o... 92

“II. “N“ nococcooouunaonounooounauoc-oouooo-noccq- 96

1W1?!“

fhie dieeertetion ie concerned with e etudy of the eolvent
extrection proper-tine of the rere eerthe. Originelly, the tern
"rere eerthe" wee diguouely ueed ee e tern for eny netel oxidee
ehout which little wee known. The deeignetion hee ultiutely
been reetricted to elenente of the periodic group Ill-A. unendiun
through lutetiu, Bophine (27) given the following definition:
"e group of netele. ueuelly trivelent, forning heeic onidee, with
oneletee ineoluhle in dilute ninerel ecide. Their fluoridee ere
eleo difficultly eoluhle, hence they any he eepereted fron other
elemente hy edding onelic or hydrofluoric ecid to their eolution
to which cone ninerel ecid hee previouely been edded. houhtleee
the noet etrihing fect which cherecterined theee elucnte ie the
reunrkehle einilerity in both the phyeicel end chenicel propertiee
of their compounde." Iron the epectroecopiete' point of view,
only elenente 58 through 70 («rit- through ytterhiun) ere included
ee rere eerthe. heceuee theee ere the only Indore which heve en
electronic etrueture involving e pertielly filled e .. f electron

euhehell .‘

Prohehly the out con-on ace of the tern "rere eerth group"
includee elenente 57 through 71 (lenthenun through lutetiu),
elthough Inny euthoritiee include yttriun end ecendiun heceuee

of their einiler propertiee. ‘l'he terne lenthenidee end lenthe-

none hove he. nuggeetod for the group of eleoeote froo eteoic
outer 57 through H to correepoud to the terne ectinidee end

ectinone for the "eocond rere eerth group" (37).

The outrun einilerity in proportioe of rere eerth coqounde
hee node the eeperetion of the group into individuel oleoente e
one: erduoue tech. nod for thie roeeon. not of the work thnt hee
hoon done with thin group of oluoete hoe hoon done with their
eoperetioo in wind.

Verieue inventigetore hove etilieed the technique of
froctiooel cryetellieetioo. frectioeel euhliontion. hono-
gneeu‘e pheeo procipitetion. ion onehenge. correction. end verioue
other oethcde u «as, to mm. acme-.1 seem of the m.
bet of thoeo uthode ere tine conning end require todioue
proooduree or oooetent ettntion. loo onehenge uethode hove hoon
ueod enteneively in the ieoletien of pure rere eerth coopeunde.
hut dilute eolutione not he ”loyed. end no yet. co-erciel
epplieetione hove been linited. ’eppord 35 9;. (46) hove ueed
eolvent entrection toehniquee with eucceee. end Hoover (73) hee
eepernted one hilogren of gedolini. oxide utilining Popperd'e
nethod. ' I

e veletile eoqeund of the rere eerthe would he out volu-
ehlo in thet treetionel dietilletion technique could he utilized.

hey inventigetore hove “tented to propere envelont ooqouede
of the core eerthe. in the hope thnt they night he voletile.

3
without eucceee. It in douhtful thet e truly covelent coopound of

the rere eerthe eniete.

delvent ontroction nethode would he el-oet idoel for e
co-erciel oethod of eeporotion. in thet. e continuoue ontrection
proceee could he utilieed. end e nini. of heme lehor would he
required. Iheoretichlly. eny odor of the rere oerthe con he
eepereted frco the renninder. in eny doeirod degree of purity, in

only two operetieoo. (l. ‘6)

'l'he require-onto for e notoriel which would ooho it euitehle
for eolvont entreetieo ere thet it he eollble in oeeh of the
.i-iecihle ecu-nu. thet it he cutie. end thet 1: he of renoun-
ehle coet. leverel good roviewo hove recently he. puhliehod on
eolvent eetreeticn in geeerel (1. 6e. 69). no no etteqt will
he node to elehorete eo thie topic here.

Since the oethod of liquid-liquid entreetion hee the
edveotege of heing cepehle of continuoue operetion with e oin-
i-In of nonpower required, it in felt thet future edveoeee in the
eeperetionel nethedo for the corn eerthe will prohohly he in thin
nee. the hietowieel eeetioo fiich followe will preeent eoverel
nethodo thet hove he. devieed for wtilining thin technique for
the eeperetionoferedenintureeofreweeerthe. hutnoetudyeoeoe
to hove hoon ado on the oeture of the entrectioo preteen. It won
fre- thie point of view thet the etedy doecrihod in thie thoeie
woo pl-od.

outcome].

1

the eerlieet non of the principle of dietrihution in the
perificetion of the rere eerthe woe propoeed hy Urhein (66) to
eeperete thoriun fron the precipiteted oneletee. Thoriun oncelete
wee redieeolved in min oeelete. which eleo dieeolved ecne
calm. the hydroxidoe. precipiteted hy genie, were euepended
in dilute elcohol end treeted with ocetylecetone. the thoriu
ocetylecetonete forned wee entrected with chloroforn, the ceriun
coepound no not dieeolvod. Jenee (32) edoptod the neth to
renove thori- in hie och-e for the eeperetion of the rere onrthe.
P. end B. Irhein (67) weed e einiler nothod in the purificetion
of eeendiun. Ioendiu hydroxide wee precipitetod hy min in
the proeeuco of e elight oncoee of ocetyleeetcne. d the ecendiun
ecetyleeetoneto wee entreeted with chloroforn. the eeperetioo
wee completed hy euhlinetien in veeoe et 100°. only the eceodiu
ocotylecetonnto heing wolotilo.

Itoddert end hill (57) inventigeted e noth of differentiel
extraction, if not e dietrihution, hy treeting rere eerth eteeretee
with verioue orgenie eelvente in n 8onhlot ontroetor. lther, elco-
hol. cerhon dioulfide, end chloroforn eetreetod only the trece of
etoerie oeid preeont. Ioneeno eueod e elight eeperetion, cerhon
totrechlorido nd xylene did initielly, but on further trentnent
dieeolved ell the notoriel, ee did toluene. nolten nephtheleno end

enthreceoe. end hot olive oil.

hernehy (5) inventigotod the eolwhilitiee of rere eerth cono
We in non-equeoue eolvente, end their precipitetion hy odding
eolutieee of inorgenie end orgenic eeide. he ouggeetod froctionel
eryetellieetion of the halo nitretee in ecetone inetoed of weter,
end noted thet the rooctione in ecetono oelution ere of the neon
generel order on thoeo in ooueoue oelution. In node no nention of
dietrihetion. however- deheeffor (53) etudied the eoluhilitioe of
rere eerth nitretee in verioee eloohole. hut did not euggeet their

con for eoperetieoe.

A dietrihution nethod for eepereting ceriun fron the other
rere eerthe wee proposed by lnro (29), who found thet the die-
trihution coefficient of ceriun (1') between weter ad other do-
pnded on the uncentretion of eeriun. the concntretion of nitric
ecid. end the reletive volunoe of other end weter. Under the proper
conditione, here then ’8 peeoent of the eeriun nny he renewed.
lelle (76) neeeured the eolfiilitioe of the nitretee of nine rerer
“acute in other. he found difficultiee heeeeee of unnertein-
tiee in hydretion. end he nontioeed thet l”other ney find cone
epplieetioo in e nethed of eepereting the rere enrthe”.

the eoluhilitiee of rere eerth chloridee in non~equeoue eol-
vente were neeeurod hy hopkine end Quill (28) who euggcetod en-
trection of the nitretee with other on e neth of removing enell

enounte of noodyniun preeent en en impurity ”in preeeodynim.

It rennined for tieeher. heite. end .fiihernnn (18) to meet

frectionnl dietrihution between imiecihle eolvente on e gonerel
nethod for the eeperotioe of ell the rere onrthe. They etete
tho: the rere eerth helidee will dietrihute theneelvwe between
weter end elcohole, ethere, end hetonee. end thet hy the proper
choice of eelte end eolwento, the difference in dietrihution
ooefficionte of eelte of two rere eerthe differing in etonic
“or hy one nny enount to 50 percent. lo dete were given to
eupport thin etetenent, end e leter review hy e neuhor of
l'ieehor'e hehoretory, loch (7), nehee no nontion of ouch e lerge
difference in dietrihution coefficiente. It in prohehle thet

Iiecher wee unehlo to reproduce the previouely reported reeulte.

Appleton end Selwood (2) found thet the rere eerth thia-
eynnetoe were eoluhle in n-hutyl echohol, end were ehle to
ohtein e pertiel eeperetion of lathnmn end neodyniun by ex-
trecting the equeoue thiocyenetee with hutyl elcohol. The en-
richnont fector for neodyniun wee only 1.06, hut they expreeeed
hope for the poeeihility of e continuoue entrection proceee.
leventhnl (36) eleo etudied the dietrihution of rere eerth thio—
cyaetoe, perchloretee, end nitretee between weter end hutyl
eleohol, hut did not heliove the neth euitehle for eoperetion.
deeolin, -bdrieth, end Coninge (3, 6) continued heventhel'e work,
ad found thet thoriu- wee eepereted fron en equeoue eolution of
thoria ad noodyniun nitretee hy oetrection with l~pentenol
eelteining mi. thioeyenete.

fealoten (el) worked with rere eerth nitretee, utilising

entreetiene with higher eleohole or hetenee. ad ta entree“.
of therewoeerthoae toad to ineroeoewithetooie nwaer.
fealetoe end letereon (65) etudied atroctione of rere eerth
nitretee. end in the eoperotion of no... end needy-tun by
atreeting the equoou oelution with e-heeyl eloohol. found the
arieaoet in needy-la to he ehout l.’ for e eiegle etege
oporetioo. loo e three etege attention, the enrieaeot wee
2M. rapier-e it u. (to. ea. to) etudiod the dietrihwtiee
of thoria eitrete hetwooo woter ad voriouo oleohelo ad

hotooee.

lienhereodhoehun pueifiedoeendiahyentreetinfrcn
egwoeue .euia thiooyeneto oelution with diethyl ether. l’ieeher
end dholyheeuo (20, ll) report e eeperetion ofeieeeoia end
hofniahpnuaeef theentreetionef the thieeyenetoo intedi-
ethyl ether. hoohend loch (d. 9) found thet eeriun. eeadia,
ad thorianitretoonnyheontrocted fronnitflo eeid eolutione
with other. court. hetoeee. end elect-lo. they etete thet eere
tha 95 penal of the eeri- ie entrectod fron I I nitric eoid.
loch ad hyer (10) report the oeperotioe of ”.5 percent eeria
with yielde of 85 percent hy eetrooting the nitretoe with diethyl
ether. Iieehor n g. (1!) report feir eopeeetiou of e crude
uinture of the rere eerthe utilieing the diotrihutiee of the rere
eerth nitreteo hetwoon eeuoouo lithiun nitreto end either diethyl
ether or lopentenone, end report entreetehilitiee of the rere
eertho to inoreeee eeeording to the following eorieo: lathawn,

ceriu, preeeodyniu. gedoliniun, neodyninn. yttrium. curiae.

dyepreeill. hohi.. erbiu. end lntetiu.

Bottle (58. 59) etudied the chelction of lanthanum end
ceriun by thenoyltrifluoroecetone using extrettiae techniqeet.
Lutheran end teriun in trecer qpnntitiee were extrectod with
bencone ooietieeo of the ohoictin; ecent tron eqeeoee eoietiono
et verioeo pn'e. loon- ond Settle (33) node oiniler etedieo
with preeoodyniu. ”Us (50) tMied copier (oration o!
ecetyleeetone with the ectinidee by e liquid-liquid distribution
technique. Braid-o (11) found that scendiun my be repeated
from the run earths in e eingle extraction with n benzene so-
lution of thencyltrifluoroecotone at n pl! of. 1.5. Bonner and
Jackton (41) determined the distribution of neodymiua end euro-
piun by extracting aqueous eointiona at high (9.6) pn'e with e
ohloroforn eolntion of 5. 7edichloro~8-quinolinol. Dyreson end
Dehlberz (14) etudied the extrettion of innthennn) retention.
amt... thorium, end ereniun (IV) nitrcte rith e ohloroforn co-

lntion of either coplerron or exine.

Wylie (76) hee enenined the extrection o! eerinn (IV) nitrate
tron 5 . 6 noml nitric eoid eolntione with other. end fond
thet ee mach en 99 percent of the oeriun in e rere eerth nixtnre
io extrected. He chorod thet the extreetod oorinn wee present
cc e nixtnro of nzceurog. end $430,390. Io ctetee that
other ooireete rhieh entrect nitrie neid tree 3 - 1 nor-i eo-

lntione II: he need.

9
legiwere (25) etudied the extreetion e! thoritn tron equeone
ecletione ntilieins lenitroeo'benylhydroxylnine dieeoirod in
verione organic eoivente. Re need other. n-hntyl eeotete, end
terbon tetrachloride. Thu bntyl acetate eyet- who etmlied noet

extaeivnly.

Her! hee propoeed the nee o! tri-e-hetyi phoephcte (70) end
nitronethae (71) for the extrnetioe of teriun (1V) eitrete. bet
theoo ooperetione do not eppeer to he on eieen no the other on-

treatiorn.

Pepper-d 3; 51° (‘6) here recently developed whet eppeere to
be e rether pro-Lune nethod tor the eeperetion oi the rere onrthe.
Theee norhere ntiiiee tria-hntyi phoophete no the non-eeueone
eoirent (either pnre er diluted with en inert hydroeerbon) end
the rere eerth nitretoe dicoolved in eontentretod nitric eoid
co the eeooone pheeo. letrectehility nee round to inereeeo with
etonie ne‘er. hot thie nee reverted in dilute (0.3 I) nitric eoid.
deendiu could he eeperetod Iron yttrinn end the rere eerthe in n
eiule eperetion by nein; the ehloridee ineteed e! the nitretee.
"never. broom. end to" (73) were ebie to ieoiete over e
hilosr. of 95 - ” percent pore redoiiniun oxide by "in. the
nethod e! rm. the oolntione need by Homer were: for the
food. 13 none! nitric eoid with 20 green of rere eerth oxide per
liter; for the equeone pheee. 10 none! nitric etid; end for the
orxenie phnoe. e so percent eoletion o! tri-n-hntyi phoephete in

 

 

10
Vereei (e ee-ereiei ornenie petreie. treetion). in e three oteu
eroeoee. the eepeeetien teeter heteeen nedeiinien end tern-none
ehent eeven. ad hotne- endoliniu ad ennui. ehoet nineteen.
leer-rd g; g. (m etndiod the entreetiee or thoriu- tree pitch-
hiade with tri-n-hneyi ybeehete. end were chin to ieolete 3r-
ennntitieo oi thoriu-nd. linerd. Grey. ad hrhee (‘5) he”
nine etndied the entreotien or the eotinidee ntilieine the one
negate. deedd. ad Mine (31) rue die to eeperete yttriu
iron the tenth. group by - entrnetion e! the eoietion rith e
0.6 neler eointion o! di-e-hwtyi yheepherie eeid in di-betyi other.

Icheeiteer end Ioott (it) doternined the entreetioe or yttri-
nn inte eeetyieeetone tree eeneone eointione et rerione pil'e. end
lteinheoh .d heieer (55. )6) node einiier etndiee for verioee
other netele. her not (or the rere onrthe. Inna-n (it) etndied
the entreetien o! eetini- eeite by e heeeeeo eoietion or thuoyl-
triflnoroeeoteno. leeneuey (it) hee otndied tho eetreetion ot
ientheun, needyniun. end uroyinn eootyieootoneteo into chloro-
lern tree eeeeeeo eeietien on c function or pl. end ton-d thet
little ditterenee in their entreetehiiitiee eniet.

lherie end Lerner (i!) eeiino the nethode or lyreeen end
w (or a eeeiytieel nethed for the deterninetioe oi eeendiu.
their nethed involved liret entreotin. the eenoone eointion with
e oeintion o! tendorroe in chioroiorn. yruipitetin. the entreet-
ed ecendien eo teetrete. end then entreetiee the eeendien tron
thie neteriei with tri-nobntyl phoeyhete tree eeneoee hyhoehiorio

ll
eoid ooletion. Lerner end Petretic (35) remove thorinn.£ran e
rere eerth nixtnre by ertrectins the bulk of the thoriun with
dibutoxytetreethyleneglyeol, end then the reeidnel thoriuniie
renoved by extracting the equeone oelution with e oelution of

sequinolinol in chloroforn.

thie hietory chore e eenplete ebeenee or eny etedy eined
et the netnro oi the prooeee involved in the dietribntion of
rere eerthe between eqeeone eolntiono end en orzenio eolvent.
The next oeotion ehonld provide the bethgroend for the point
of View tehee in the deeign of the etudy presented in thin

theeie.

12

THEORETICAL

Irving. Ioeootti. end Willie-e (31) hove preeented e very
generel treetnont on the oolvent extreotion oi inorgenic cor--
pounde. end noot oi the neteriel in thin nettion nny be enpli~
died by ooneultin; their poper. cleeoieelly, the einploet type
of pertition between two i-iecible liquido in given by the
lornet pertition low: (1)., i ,(x), where (1)9 repreeonte the
concentretion of 1 in the orgenic phone, end (I) reproeente the
concentretion of r in the eqeeoue pheee. Should I be poly-er-
leod in the arsenic photo to e epociee X“. which in not per-
titionod iteelf. then (In), I “no‘. If (x90 1e nth greetor
then (3),, then the dietribution retio, q, ie given by the
following equetion:

q - moon/(z) . mm‘ ' 1.

Thie equetion impliec thet the gredient of e logerithnie plot of
q (experinentelly doternined) ve'reue (X) will give the degree of
polyuritetion of r in the ornnio phone. Inch oinpiicity ie
not gonerelly the once for inorganic eyetene, however. In there
eyetene the ectuel opeciee which any croeo the phone boundary

my be only e ninor component of n very couple: eyetou.

Iirot, lot at one-inn the equilibrie exietin: between the
cinple ione end oil of tho verioue epocioe which any nehe up the

eyetnn of two reletivoly ie-ieciblo liquid pheooo. Itoy equilib-

 

13
rie con be need to deecribe the concentretione 0! different
epeciee oxioting in the equeoue pheee. end e eerioe of partition
coefficiente weed to relete there concentretione to than in the

orgenio phone.

If we coneider en equooue eolution which in in equilibrium
with e roletiwely i-iecible orgenie oolrent, I. end eontcine
notel ione. I“. hydrogen ione. l+, ad enione. I". end if we
eeouno thet hydrolyeie oi eny oi the eetionie eyecioe preoent
ienot epyreeieble, ell the coupler lone; eeidoocpeoioo, end
polyuclenr opetioe which night “int in etep equilibrie eon be
royreoontod by e gonerel tern “h“(‘zmw'e’ end their concen-
tretione reletod to thooo oi the oinyleet iono by e eeriee oi

ovorell equilibriun tonetento defined on follower
kltnwe ' (thhldfiflhle)/(3).(n'(fln(nz°)'“)‘g (I)

where h. n. n. w, end o reproeent tho n-her of hydrogen ion.
netel iono.~ ligend lone. wetor noloculoe, end eelvut noleculee
eeeooieted with the eqlu. tertition eoeiiieiente tor eech of
the yoeeible epecieo ere defined by

M ' "h'n'n('2°)w'o)o/(Wn“i°)w'e)a ‘2)

where the euhecript o it need to dietinguieh the orgenio pheeo
iron the equeoue phone. A gonerel dietribution retio ney be

written not

14

‘ . totel cmgtretion of motel in the orgmg ghee;
totol eeuntreti. oi netel in the eeweeee phone

. W
2 “h“ 320)w5o)
. W . m

2 ‘(fl‘fllfl)’ I)
where the emotion includee ell yhyoieolly oigniiieent codi-
netiono oi h. n. n, w, end e. fhie «notion ney be oinliiiod by
oneleding terne iron the nnoretor in which M to oeuel to
oero. conoidoretiono oi oleetroneutrelity roeeiro the oeclueion
o! the dietribution oi eherged epeeioo. end inoee the condition
no .+ h - or. the evorege eowoeition of the diiioront oyeeieo in
the equoono pheee ney elweye be ropreoented by e oingle eyflol.
_w__i_.e_.. may)“. where I rcproconte the polyierieetion
outer. end 5 end a the m... number of hydrogen end ligond
otone er lone per etc. of motel. end 6 end 3 repreont the overege
other oi wetor nolooelee cod oolront nolooeloo per eton ot notel.
The obove oeuetion (3) my new be written in the torn

e ' MW<HzO)WoIt(Wmlfifii
55m ‘ moi“ Ramofiflbfi ,
10"“) (320)m’(8)m'
lepreeeing erection (e) in logeritbie torn. we here
he . - hush/E) + ton-1.13) + (‘o‘o - 35mm)
+ (i. - anon-o . (503. - 32mm
+ flo'e - 0) log(H29) t (ioio - 1“) loci!)-

      

(5)

15
If the ionic etrensth ie kept conetent. end (I) endale) ere
hept conetent, end provided there in no cheese either in eolwetion
or in the eolwent proportion of the two pheeoe, the leet two torne
of the ehowo eqnetion ney he conbined with the tint tern to give
10: 1 ' A . Ion-ole) 4* (Sofie - 35mm“)

* (5o - {bloc (IO 0 (Sofie - Snot“). (5)
where the torn A in independent of (I). (I). end (I), end cen he
elininetod by differentietion. Iy yertiel differentietion, the
theoreticel neenin; of the elope of the lonerithnic plot of the
extrection coefficient venue the concentretioe of Intel, ligend,
or hydrogen ion ney he ewelneted. 'fhe pertiel differentiel with
roepect to the logerithn of free ligend concentretion io equel to
(long . II), the pertiel differentiel with roepoot to the loxerithn
of free netel ion concentretion ie eqnel to (So - i). the welne for
the werietion with reopect to hydrogen ion concentretioe ie coupe-
rehle to thet for the ligend concentretion, being (Itch, - :5).
l'hoeo onentitioe reyromt the difference in the ewerese nnfler of
ligend ione, notel icon, or hydrogen ione eeeocieted with the con-
plee in the ormic pheeo end the eworeee elder euocieted with

the couple: in the equeone pheeo.

'l’ho merinonte deecrihed in the next eection of thin theeie
were deviled to give the type infornnt ion neceeeery to neko the
kind of enelyeee deecrihod ehowo. rho thiocyenetee were chosen
for etndy hecenoo it wee felt thet eince the thiocyenetee of my

of the treneition notele ere entreetehle fron eqneone eolntione by

16
organic nolventn, the thiocynneten of the rere eerthe night elno
prove to he extrected. Tri~nvhutyl phonphete wee chonen en the non~
eqneoun nolvent hocenno of the enccennful one of thin nolvent for
the extrection of rere eerth nitreton (66).. The concentretion
reason were chonon for etndy fron the point of view of onefulnene
to en indoctriel nrocene. It won felt thet en fow'veriebloe nn
poenihlo nhonld he introduced, end for thin roenon, the effect of
dilution of the tri~n~hntyl phonphete with en inert hydrocerbon
wen not ntndied. With thin hecksronndywo' ney now proceed to the

expert-entel noction.

l7
nmnnmt

in order to etilino the theory of Irving 3; 51., the din-
tribntion ennui-onto dencribed here were donigned no on to leern
the effentn of the verionn verieblen of the nynten: rere eerth
eonnentrntion. thiocyenete concentretion. end the ecidity. leper-
inentn were perforned in which two of theno verieblen were kept
conntent, end the third verind. In thin wey, the effect of eech
individual verinble wen neenwred. In the prenontetion which
follown. the enporinente with eech rere eerth ntndied ere pronento
ed together, no ell extrection detn concerning lenthenun will be
found in one nection, whereen thone concerning neodyniu will be

found in ennther, etc.

Mnfimmm

Quentitetive work on the rere eerthn often necenniteten ever-
ege etonic weight deterninetionn of the perticnlnr nenplen being
need in order to entinete the purity of thone who. The nml
nethod for thin doterniution in to find the onelete to enide retio
(in). thin «not be done by the eiqle ignition of the onelnto.
becenno the rere eerth onnletoe do. not eerily becone enhydroen.

The nethod emlly enployed to obtein thin retio in to find the
percent onelete in e mle by titretion with ntenderdined por-
neegenete, end the percent rere eerth oxide by niqlo ignition.

The everegn etonin weight in then celcninted en follown: A

13

" °"“‘”‘ n wt onelete titreted mango:

M
zg.3..g_t_%g;nte ignited
. In Mnnllhngnnen.wtof¢103

Mme eerthnnnodfor thinocndywere ell fro- the
Iinhig. ante Iniwnrnity ntonh. 'i'ho everege ntenic weight of

 

the lenthemn wen lid... Ironhly ignited lenthe-n enido nfilen
were perfectly white. ‘l‘oete for neri. were motive. end len-
the. nelntiene nhewed no ebnorytien h-de for other rere onrthe.

:‘lhoflneodyni- bed on ewernge etuie weight of 1“.“ end the
freon! Wind enide wen pele hinn in eel“.- Donation npeetre
of the needy-inn nolntienn ehow hot nlight eheorptien in the
regionn nhnrecterintie for both nenoedyni- end eennriu. the
enonnt oftholeo. two rere eqtbe prenent. however. wen inneffieient __
to effect the neennn'eneue nde neing thin neteriel. the eh- .
norntionnpeetrnnof thenonidynieneeed in nhouee Iignre l. the.
newts-twee tehnn on e loch-en nodel 91.4 recording npeetro-
photonntor enieg e one dentinetor eell. end e nolntion 0.15 fornel -
me roepoct to needy-inn. , run. [for neri- were negotiwe.

minteeoodyninn notorielhed been nnrehenod fr- thn bindeny
Mole-nyendnnneodeden the”... poreent Kennedy-ia-
oxide (bindney cu- m). an mm wee hhnnh a color. end e
yorehlorete Innlntioe geve en eheorption npontrnn which hed no
obnorption bade for other rere onrthe. the ebeorytien opener.
for the unneedyninn need in cho- en tignro l. the nneetr-wen _
tnhon throngh n one nentinetnr enll, «in! e nolntiee‘kl.“ foennl
with rennont to "w.

00Nx 000\

L

n

0.00 0.0K 000

._.....

\MWW. CBCQOthS
0“ 00‘ Rn.

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ED‘tUQO CDQDCOWQ V.
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afinflk ttufinuxfifin

 

 

 

 

 

 

 

 

 

 

 

 

 

 

00Nx 000x 000 00k 000 0‘? 00». 0k». 00M. 0MM.
. b . F _ _ . p . . n . _ p . p . _ n n b . . _ Q
2 I0\
I0N
6n .4.
o
MNVORVVKQ .\0 .05. w
COtQOm I..n\\.0 0 .x0 4
“.950QO £0:onqu you u.
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9.
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21
The freehly ignited neneriun oxide wen pele creen in color.
The ehnorption npcctrnn ehowod no ebnorption bandn for other rere
eerthn. The ebnorption npectrnn of the nemriun need in nhown en
figure 3. The epoctrun wen tekon through e one centineter cell,

inning e nolntion 0.2 fornel with reepect to nennrinn.

hero gerth Thiocznneten

'l'he rere eerth thiocyeneten were propered by the netetheticel
reection of beriun thiocyenete end rere eerth nulfete. the pro-
codnree were eenontinlly the nenn in ell cenen. encept thet in one
enne oryeteln of the compound were prepnred, end in the rennindor,
the nolntion wen need no ouch. 'i'he proceduren for uni: cene ere

dencribed lnter.

loodzginn Ihioczeneto

‘l‘he preperetion of needy-inn thiooyeneto in cryetelline forn
nterted with ninty-five green of neodyninn oxide dinnolved in
thirty-five nillilitern of concontreted nulfnric ecid which hed
been provionnly diluted to ebont 750 nillilitern. In order to
dienolve ell of the neodyninn nolfete, thin nolntion bed to be
diluted egein to e volnno of npproninetoly four litern. The no-
lntion wen then filtered. One hundred nixty-fivn grene of berinn
thiocyenete wen dinnolved in ebont 750 nillilitern of weter, end
both thin nolntion end the neodyninn enlfece nolntion were heeted
to elnont boiling. the berinn thioc‘yenete wen then edded nlowly

to the neodyeinn enlfnte nolntion. end thin'wen then ellowed to

00N< 000x 000 00k 000 00%.

p

L. ...PL...

0“

{$08.08th

 

P b

 

 

 

nxroxoyftm. K0
CDCQOW ..u\\.0 .0 k0
E3}. OWQW 8.... QKOMQG‘
M: mklflfix

 

 

I
0
0

I j
0
u 9.
uo.ss,x.usuo.4_4 rue OJOd

é

fi00

 

v00\

 

23
cool. The herinn enlfete forned wee removed by filtretion, end the
filtrete euporeted to e wolnne of epproxinetoly one liter on e
nteen both. It wen further oweporeted by piecing the nolntion in
e cryntellining dinh, end plncing thin in e deniccetor over con-
contrnted nulfnrio eoid. end the deniccetor nvecneted. lot until
the volnne of the nolntion hed reeched ebont 125 nillilitern did
eny erynteln begin to nppeer. lweporetion wen continued until e
feir enonnt of nryntelline noodyninn thiocynnete hed for-ed. 'i’hin
neteriel wee collented by filtering, end the crynteln were tehon
up in 250 nillilitern of Mtiwity weter. thin nolntion wen
then nnelynod for neodyni- end the fornelity wee found to be
0.572 with reepect to noodyninn. the nolwtion wen enelyned en
followez twenty-five ndllilitern of the oelution wen diluted to
250 nillilitere, end twenty nilliliter union of thin nolntion
were pleced in 250 Idlliliter henhnrn. diluted to ebont 100
nillilitern. ecidified. end heeted to elnont boiling. not on-
elic ecid‘wee then edded to precipitete the noodyninn en neo-
dyninn oneleto. the neodyninn onelnto wen collected on Cerl
Ichleicher end schnnll white ribbon filter peper. dried. end
ignited et 9750c. in pletinnn.crnoihlee. the enelytieel dete

ere given on 'fehle l.

24

 

 

25212.1
Ahnflznénzsiuasiiszza.225:§i22.£2r.!22212£na
weight «203 . fornelity
0.1920 0.5111
0.1920 0.5123
0.1920 0.5129

the thiocyeneto content wen enelyned by titreting two nilliliter
union of the ntoch nolwtion with 0.100]. eilver nitretn no-
lntion. nning eonin en, indicetor. 'l‘he fornelity of the nolution
with renpect to thiocyenete wen 1.51. the enelyticel dete for

thin deterninetion ere given on reble II.

 

 

 

Ieble H
.Aasixri34nlJEMUHEDULlaissisnnistuihissznnns:
30.30 1.515 .
30.20 1.510
30.20 1.510
.innstnnnnizhieszsness

Leathenwn thiocynnete wen proper-ed by oneentielly the nene
nethod en wen need for the neodyniwn nelt. enoept thet nore cere
wee need in the weighing of the lenthenun oxide end the berinn
thiocyenete, end in the nnennrennnt of the enonnt of enlfnrin
ecid need. the nolntion rennining eftor the berinn nnlfete wen

ronovnd wen not oveporetod to erynteln. but only tehnn down to

 

25

e volume of npproninntely one liter. The solution wen enelyred

by the nothod deecribod for neodyniun, except thet it wen necnnnery
to digent the procipitetod lenthnnnn oneleto over e hot plete for
e period of ebont two hoorn in order to coegnlete the precipitete.
end ninplify the filtretion. The nnelyticel ronnltn ere lintod

en rehle III .

 

 

l'eble El
Anelyni! 3; 29.9513 golntion _f_g§ anthem»
Height “203 g fornelity
0.0737 0.0525
0.01“ 0.0567
0.07“ 0.0567

 

'i’ho nolntion wen nnelyned for thiocyenete by tehing five
nilliliter engine of e nolntion node to be 0.205 fornel in
lenthennn, end edding nilver nitretn nolntion. ‘i'ho nilver thin-
cyenete precipitete wen digented on e hot plete for ebont two
hoern, ellowed to cool. end then-collected in weighed pyren
fritted type gooch cruiblen. the fornelity of thiocyenete which
nhowld be preeent would be 0.615, the fornelity obteined by ennl~
yein wen 0.6138. which in e roenoneble check for the theoreticel
enonnt thet nhonld be prenent. 'fhe enelyticel reonlte ere givon

en 'l'eble IV.

26

Table IV

 

Analzaie‘gg LaSSCNzg Solution for Thiocgnnnte

 

 

weigh: AgSCR FormaliEE
0.5092 0.6136
0.5095 0.61100

 

Prneeodjnium 'miocyanggg

Ireneodyndwn thiocyenete wen propered by dinnolving preneo-
dyniun oxide in nnlfnric ecid, ellowing the prenoodyninn sulfate
to cryntelline, filtering off the nothor liquor, end tehing up the
crynteln in conductivity wetor. Thin oelution wen then analyzed
for preneodyninn‘by the none method en described for neodymium.
A.beriun thiocyenete eolntion wen node from C. r. grede barium
thiocyenete which bed firnt been recryntellined from ebeolnte
nethenol. Thin nolution wen enelyeed by titrnting with ntenderd
nilver nitretn nolntion, uning ferric nitretn en the indicetor.
Iquivelcnt neonate of the prnneodyniun nulfete nolntion end the
beriun thiocyenete solution were edded to one another, end disen-
ted for epproxinetnly four honrn on e hot plete. The procipiteted
berinn nnlfete wen removed by penning the nolntion through e fine
frit. end the filtrete wen evepornted to n volume of epproxhnetely
250 nflllilitorn. Thin solution wee then nnelyned for preneodyninn
en described before. The nolution was found to be 0.284A formal
‘with respect to presoodyninn. Preeaodynium perchlorete was pre-
pared by nprinkling preneodyniun oxide into perchloric acid, and

ntirring over night. The encore preneodyninn oxide wen filtered

27
off. end the pl of the nolntion wen neennred end found to be ebont
0.5. Thin voice for the pH in on the ecid eide of eqnilibrinn, end
then innnron e nininnn of beeie preneodyniwn eelte, end elno e

nini-nn of encecn perchloric eoid.

m Eioczenete

Mien thiocynnete wen propered by the none nethod on do-
nnribed for the prenoodyniwn cowpownd. i'he oelution wen enelyeed
for eennrinn by the none nehtod en nee doncribed for the enelynin
of needy-i. thiocynnete, end the oelution wee fonnd to be 0.325

fennel with neepent to enneriu.

lxtrnction 2; here berth zhioclenetnn by m-g-butyl

on hete

the nolntiono deeorihed below were node by edding the proper
tenet of the nteeh rere eerth thiocynnete eolntion. etenderd.
perchloric ecid eolntion to edjent the ecidity to the deeired
velno. either .oni. or nodiwn thiocynnete nolntion to edjnnt
the thiocynnete concentretioe. end conductivity weter to bring
the totel eqneonn volnne to the deeirod velne. (for the erect
contonto of oech eoletion. nee eppendin). A volnne of tri-n-
bntyl phnnphnte eqnel to the totel eqnnone vole-e wen edded, the
eontninnrnhehen.endthopheneeellowodtoeeperete. Inor-
den to encore ennilibri. condition. the two phonon were ellowod

to rennin in content for ct loeot eirteen been. the tri-n-

28
hutyl phonphnte need wen purchcned fron the Weird Solventn
Conpeny, end before one it won wenhed with nodiu cerbonete col-
ntion to remove eny nono- or di-bntyl phoophoric ecid which night
he prenent, end then wenhed ten tineo with conductivity weter. 'i‘ho
nolntionn were enelyned by tehing nnplee fron eech phone. edding
ebont 75 nillilitnrn of voter, booting to elnont boiling, end edd-
ing hot onnlic ecid. 'l’ho eolntione were then ellowed to cool. The
rere eerth onelete wen collected on Cerl ochleicher end Schuell
white ribbon filter pepor, end in the cone of the orgenic phone, it
we neceenery to wenh the filter pepor et lecnt three tinoe with
nethenol or ecetone in order to renove ell the tri-n-bntyl phon-
phete. Unnelly. the precipitete wen wenhed twice with nethenol
end then twice with ecetone. dried. end then ignited in pletixvnn
crnniblen at 975° c. It nhould be noted thet when pletinnn were
in need et theno tenperetnree for long pcriode of tine the ernoio
blee lone none weight. end it in neonnnery to weigh the crucible
often renoving the oxide by wenhing with dilute hydrochloric ecid

to ohtoin the torn weight.

553.555.2225....12.“ “W

the effect of vnrying the ecidity of the initiel nolntion
wen ntndied by deter-icing the diotribntion coefficientn of
needy-i. thiocynnete et different initiel ecidition. while the
needy-i. thiocynnete eoncentrntion wen held oonotnnt ct e
fornelity of 0.100. Teble V prnnentn the rennltn of thone on-

tree t ionn .

29

 

 

 

 

191: 1
W £22: £2: mg
Concemtgegioi in £13?“ 23; Liter?“

ha Nd Acidity 1%.
lo. 011.3931 Originel 5:4 eon; figuic

1 0.100 0.101 0.0355 0.0017 0.876

I 0.100 0.300 0.0773 0.0170 0.312

3 0.100 1.009 . 0.1010 0 0.0116 0.120

A ._

1t mey be eeen from theee reenlte thet the dietribution
coefficiente decreeee ee the initiel ecidity ie increeeed. or thet
the dietrihution coefficient hee en inveree dependence on the initi-

el ecidity.

“the effect of chewing the thiocyenete cenoeetretiee wee etud-
ied hy vex-yin the emoent of thiocyenete while the connotation of
neodymium end the ecidity were held conetent. In order to edjuet the
thiocyenete concentretion to the deeired veluee, etenderdieed
nonin- thiocyenete eolntion wee edded to the mixture of neodymium
thiocyeeete end perchlorie ecid. The totel volume of the equeoue
eolctien wee edjneted to twenty millilitere by «an; the proper
emownt of conductivity weter. Twenty millilitere of tri-e-butyl
phoephete wee them edded. end the conteinere were ehehen end the
pheeee ellowed to eeperete. rive milliliter eemplee were removed
from eech pheee end enelyeed for neodymium ee deecrihed ehove.

the reeulte of theee enelyeee ere preeented ee rehle VI.

Table 11

sxtrggtion gete for m
Concentretion in 1101;; nor Liter W
Id

 

 

 

Inn Id Acidity 80! Id
. incl 1 0: u en c
5 0.100 0.101 0.273 0.0501 0.0099 0.921
6 0.100 0.101 0.308 0.0077 0.0558 1.17
7 0.100 0.101 0.353 0.0012 0.0619 1.50
0 0.100 0.101 0.700 0.0102 0.0927 9.06
. 9 0.100 0.101 0.002 0.0280 0.0757 2.71
10 0.100 0.101 0.531 0.0190 0.0032 0.37
11 0.100 0.101 0.620 0.0138 0.0927 6.06

A. ._1

 

It mey he can from theee dete thet the dietrihutioe coef-
ficient increeeee with en increeee in the initiel thiocyenete con-
eemtretion. 1t mey be 0110er then, thet the dietrihution of
neodymime thiocynnete between water end tri«n~hutyl phoephete ie
dependent upon the concentretion of thiocynnete preecmt in the

equeoue nheee .

In order to leere whether there wee eny eppreciehle diuer-
ieetion or eeeocietion in either pheee, the effect of the con-
centretion of neodymium en the the dietrihution wee etudied. In
order to etudy thie effect, extrectione were mede et two other
initiel neodymium concentretioee. the procedure wee the come ee
before. emcept thet the volume of eech pheee wee increeeed to
forty millilitere eo thet ten milliliter eemplce could be teheu
the reeulte of theee extrectione ere preeented ee

for enelye ie .

ral. VII.

 

31
122;: 11s
Eugen» 953 £95 mammal.
ggggcntration in Hole! #2:; Liter

 

~—

 

Ien Id ecidity 00! Id Id

:2: Origine; Original Originel Agueoue Organic 3
12 0.0713 0.101 . 0.109 0.0033 0.0286 0.631
13 0.0713 0.101 0.223 0.0303 0.0303 0.902
10 0.0713 0.101 0.270 0.0313 0.0000 1.29
13 0.0713 0.101 0.367’ 0.0206 0.0306 2.03
16 0.0713 0.101 0.036 0.0100 0.0372 0.07
17 0.0713 0.101 0.303 0.0006 0.0613 7.11
10 0.0713 0.101 0.630 0.0030 0.0631 10.0
19 0.0029 0.101 0.113 0.0329 0.0110 0.333
20 0.0029 _ 0.101 0.137 0.0269 0.0167 0.622
21 0.0029 - 0.101 0 202 0.0213 0.0219 1.02
22 0.0029 0.101 0.206 0.0162 0.0267 1.63
23 0.0029 . 0.101 0.291 0.0127 0.0306 2.01

 

theee dete indieete thet for coal initiel ecidity end thiocynnete
concentretion, the dietrihution coefficient increeeee with decreee-
in. neodymium cencentretion. the dete preeented in rehlee '71 end

V12 ere preeented erephieelljt ee-.1'1.30:e"0.

While performing experimente with lenthenum (eee below), it
wee ebeerved thet elnsnien thiocynnete wee entrected into tri-no
hwtyl phoephete to e greeter extent then wee the eodium eelt. 1t
wee eleo oheerved thet 1enthenum.perchlorete wee entrected even
when there wee no thioeyenete preeent. Another eeriee eein; neo-
dymium wee etudied with en ettempt or controlling the ionic
etreneth mede. end in which the thiocynnete concentretion wee ed-
jueted*with etenderd eodiwn thiocynnete eolution. the reeelte of

thie eeriee of entreetione ere given ee 'i'eble 7111. end preeented

:rephicelly ee Iieuree 3 end 6.

T0,): :00. m®\0fikw COQUKKCmoOCOO meCOXUoctnh

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33

 

 

 

Table ELI
gtrection beta 53; noodmum

W ncentretion in no or Liter

run ed Ac idity see 114 Ed

lo. Or in in 01:1 in noon Or an
20 0.103 0.101 0.000 0.0667 0.0360 0.500
23 0.103 0.101 0.173 0.0069 0.0530 1.19
26 0. 103 0. 101 0. 362 0.0207 0.0700 2.50
27 0.103 0.101 0.562 0.0133 0.0890 6.72
20 0.103 0.030 0.362 0.0106 0.0001 0.32
29 0.103 0.202 0.362 0.0003 0.0500 1.32
30 0.103 0.500 0.362 0.0706 0.0270 0.350

A A 4 _L

letrection of Lenthennm nioczenege

Leathenum eolutione were propered in the menner deecrihed
ehove. the totel equeoue volumee heing twenty millilitere for
the 0.1 end 0.10 formel eolutione. end forty millilitere for the
0.07 end 0.00 fornel eoletione. The enelyeee were performed ee
deecrihed ehove, encept thet the precipiteted onelete wee ellow-
ed to digeet for epproeimetely two houre before the eolutione
were removed from the hot plete end ellowed to cool. The ignition
of the onelete wee done in pletinnm crueihlee et 975' c. or ebove.
‘i'he reeulte ere eimiler to thoee for the neodymium eolutione. for
the 0.11 for-cl 1enthem1m «:1». 1enthenum perchlorete wee need
in plete of the lenthenum thiocynnete. end ell the thiocynnete
preeent wee edded in the form of mine thiocynnete. The inn-
thenum perchlorete eolution wee propered by edding en exceee of
lenthenum oxide to perchloric ecid, etirring over night, end re.
moving eny remeining oxide by filtretion. the pl! of the reeult-

ilg eolmtion wee meeeured end found to he ehout five. thie velue

36
for the pa inenred thet very little of the lenthenum wee preeent
in the form of heeic eelte, eince it 'ie on the ecid eide of equi-
librium, end eleo reprceente e minimum enceee of pcrchloric ecid.
‘l'he eolution wee then enelyeed for leethenum by the method pre-
viowely deecrihed end wee found to he 0.2700 formel. the dete
for e “or of lenthenum extrectione in which the motel con-

. centretion wee held conetent while the thiocyenete concentre.
tion wee veried ere preeented in ‘l'ehle Ix. (lote thet four dif-

ferent lenthenum eoncentretione were etwdied.)

With the exception of the 0.10 formel leethenu dete, thoee
reewlte ere quite eimiler to thoee for the neodymium. Additionel
enperimeete were performed (eee below) to expleiu the verietion
of the 0.10 formel eolution from the veluee of the othere. The
dete preeented in thie teble ere repreeented grephicelly in .
Iignree 7 end 0.

37

 

Tehle‘Lg
figtrnction 23:. £25 m
onccnt eti in Hblee r L of 0
III he Acidity 80] Le he 0
no. ggiginel Qgiginel 91301233 gagggge Qggggic
1 0.103 0.101 0.300 0.0309 0.0090 0.900
2 0.103 0.101 0.397 0.0010 0.0632 1.50
3 0.103 0.101 0.006 0.0200 0.0720 2.53
0 0.103 0.101 0.575 0.0216 0.0005 3.72
3 0.103 0.101 0.660 0.0169 0.0050 3.10
6 0.103 0.101 0.733 0.0131 0.0902 6.07
7 0.0603 0.101 0.203 0.0000 0.0250 0.570
0 0.0603 0.101 0.277 0.0337 0.0353 1.06 -
9 0.0605 0.101 0.339 0.0260 0.0026 1.60
10 0.0605 0.101 0.020 0.0179 0.0306 2.03
11 0.0605 0.101 0.317 0.0122 0.0360 0.61
12 0.0000 0.101 0.120 0.0312 0.0093 0.299
13 0.0000 0.101 0.191 0.0231 0.0173 0.750
010 0.0000 0.101 0.290 0.0102 0.0190 1.93
13 0.0000 0.101 0.307 0.0000 0.0315 3.77
16 0.0000 0.101 0.520 0.0002 0.0336 0.01
.017 0.139 0.101 0.203 0.0673 0.0730 1.09
‘0010 0.139 0.101 0.303 0.0559 0.0036 1.50
*‘19 0.139 0.101 0.000 0.0059 0.0926 2.06
0*20 0.139 0.101 0.090 0.0301 0.1017 2.67
0‘21 0.139 0.101 0.603 0.0297 0.1090 3.60

*‘An error wee nude in the eddition of tri-nébntyl phoephete,
in thet for thie entrection 60 millilitere wee edded in-
eteed of the 00 need for the reneinder of the eolutione.

*0 tor thoee eolutione, ell the thiocynnete wee edded in the
form of e-nonium thiocyenete. end the lenthenun wee edded
in the form of lenthemun perehlorete.

 

the thiocynnete concentretion for rune one through five. nine.
end eleven were deter-fined hy precipitating the thiocynnete with

eilver nitrete eolution, end.weighing the precipitete. the con-

«\muxxx £00. 000E»

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centretione ohteinei ere given ee 2ehle x.

rehle g

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wanna 22.22 m £2! m mama

 

Encentrgtioe in Hole; get Liter Organ?

III 00' 06' SCI ll/Ifll
. in e it ti
1 0.300 0.1082 0.1967 3.93
2 0.397 0.1007 0.2002 3.80
3 0.086 0.1902 0.2850 3.95
0 0.373 0.2005 ‘. 0.3276 0.07
3 0.660 0.3025 0.3503 0.10
9 0.339 0.1903 0.60
11 0.517 0.2609 0.73

 

An exeninetioe o! theee dete fine the i-preeeion thet
the thiocyenete to rere eerth retio in the oreenie yheee ie

proheh 11 (our .

An eminetion of the dete for the 0.139 fornel len-
then. eoltttione indicete‘ thet the ionic etrength of the eo-
1utioee pleye e not tninportent role in the eetrectioee. It
would eee- thet if one «I16 control the ionic etrensth of
the Inter eolution etter eetreotioe to eoee eoeeteet velue,
the resulte mid he eore neerly coeperehle. for thie pur-
poee. eevere1 note rune rere neee in en etteept to control
the tonic etrensth. thie neceeeiteted eone perhepe rether
dreetio eeetnptione. There eeeueptioee ere: firet, thet
everything ie totelly ionized in the equeoee pheee, end eee-
and, thet einoe it eppeere thet four thiocyenete lone ereee.

the pheee houndery for eech leathemne (eee tehle 2). the

Q...
ID

41
(eoreeee in ionic etrength from that of the originel eoiution would
he levee tieee the concentration of leothaown in the orgenio pheee.
Doing theee eeeueptione. the ”ionic etrength" of the eqeeoue pheee
elter extreotioe ten he celouleted. The next eeriee of experimente
rere perforeed ee previously deeorihed, except thet the dietrihe-
tioe ooeftioiente were eetheeted end the ionic etrength of the orig—
ieel eolntion wee oelcoleted to give e finel ionio etrength of
epproxinetely 0.5. I! the resulting dietrihution coefficient wee
quite eifferent fron.thet eetieeted, another estimate wee nede,
end the experieent ropeeted. the results of theee experiments
ere given on table ll, end preeented graphioelly ee lignree 8 end

lheee dete ere e further indicetion o! the importenoe of the
ionic etrength on the distribution of the rere eerthe. end they
eleo indieete thet the eieerepenoy in the 0.14 (creel lenthenue

dete previonely reported.vee hecenee of ionic etrength differencoe.

62

 

 

 

S.» 636 2.6 336 886 «26 ~26 .336 2
an.“ 636 .86 836 336 8...... ~26 836 on
36 26 ~36 236 .266 636 ~26 386 R
~n6 266 6:6 386 .386 6 ~26 «26 on
36 :36 ~3.~ $86 386 686 ~26 .26 an
2:... «$6 ~3.~ «636 236 866 ~26 226 3
B.~ 2.6 366 «$66 $86 636 ~26 «26 an
36 636 2.6 236 8.36 626 ~26 .26 an.
32 636 ~36 836 386 636 ~26 ~26 ~n
8.... «:6 ~22 $.26 :36 8.6 ~26 626 on
26 236 ~26 886 236 :36 ~26 «26 2
3.~ :36 362 286 386 626 . ~26 626 2
3.~ «$6 «86 836 $86 ~26 ~26 .26 2
~66 «36 e~.~ «~26 $36 266 ~26 .26 on
$4 266 634 $86 236 :36 ~26 .26 2
-.~ «36 ~26 286 3.36 266 ~26 .26 3
~86 «96 266 336 6266 ~26 ~26 «26 nu
2:6 2:6 ~26 236 336 . ~26 ~26 .26 «a
7...: 1.5526 3.366 382.1 11016 . T2. «To; $5.58 new.

a J 3 so» 5333 3 Ba

 

no .33.— u e933

 

 

eon-dun: mum. 33 no. «uueudmm
mm 35...... A

«\mthx L8 WQOPS Cfltflkxtmognu mxngfinuflfh
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3903.6me $285? $3

.8 t BEES 658$. 6.86 .. w
Bkflhtmnutoo MBCOXUOFR
k0 CDCOCDK .0 WO 1 k
E3C0£COJ .5 CD: 3:..th
m what

 

 

.zualaweoo 440.4on 3.10

M
In order to adjust the ionic strength of the 0.07 formal

solutions, eome ammonium perchlorate or sodium perchlorate would
be necoeeary in addition to the other salts. It was decided to
use the sodium eelt for the complete eeriee. end elso to nee sodium
thiocynnete ineteed of the mine eelt in order to reduce any
hydrolysie etfecte to e mini-m. The 0.4. 0.5. end 0.6 tor-e1
thiocyenete eolntien wee run with both the mine eelt (run
nun-here 37, 30, end 39) end the eodine eelt (ton eon-here 52, 43,
end M). 'l'he dete for theee eolntioee. ee well ee re-rune eeing,
eediu eelte tor the 0.1 end 0.11. tot-eel leetheeue ere preeented
ee ran XII. end given in grephicel fore in figure 10. Included
in 'lehle m ere dete {roe e eeriee o! extrectione enede tron 0.1
tor-e1 leetheu- eolntiene, with the thiocyeeete coecentretion
held et 0AM for-e1, hot with werying initiel eeiditiee. Theee
dete ere preeented grephicelly ee figure ll. the dete preeeeted
here indieete thet the etteete of the ecidity, leethenoe concen-
tretion, end thiocyenete eoncentretion ere of the one order ee

wee found for neodymium.

45

table m

gxtrection Deg; g2; Lenthenum

Concenttetion in 1101;; oer Liter of

 

 

Inn Le Acidity 868 Le Le e
lo. __~ the! art ' 0:1 inel neoue 0r en1o_A

40 0.0685 0.101 0.200 0.0207 0.0481 2.32
41 0.0685 0.101 0.300 0.0152 0.0535 3.51
42 0.0685 0.101 0.400 0.0109 0.0579 5.30
43 0.0685 0.101 0.498 0.0076 0.0610 .8.02
.44 0.0685 0.101 0.600 0.0053 0.0632 11.84
45 0.103 0.101 0.200 0.0413 0.0614 1.49
~46 0.103 0.101 0.400 0.0283 0.0744 2.63
47 0.103 0.101 0.500 0.0174 0.0853 4.90
48 0.139 0.101 0.200 0.0782 0.0612 0.783
49 0.139 0.101 0.400 ' 0.0525 0.0869 1.66
50 0.139 0.101 0.600 0.0284 0.1110 3.91
51 0.103 0.050 0.400 0.0214 0.0813 3.80
52 0.103 0.101 0.400 0.0283 0.0744 2.63
53 0.103 0.202 0.400 0.0451 0.0576 1.28
54 0.103 0.504 0.400 0.0759 0.0268 0.353

 

the concentretione o2 thiocyeoete to the orgenio pheee were

deter-teed for zone 46. 47. 49. 51,53. end 54 by precipitetin; the
thtoeyeeete‘with eilver nitrete eolution, eed‘weighin; the precipi-
teted etlver thlooyeeete. the veloee obteioed ere elven ee teble

XIII.

 

3.0.3 100. mmxnué COEUKxCGUCOD meC0>\00\C|h

.06 “6 V6 M6 N6 \6
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$26th 5.8% S}
8 B b.3886 $886 6.3%

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3 4.6 no No B o
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an
Egg x111

Extraction data for SCH from Ln‘SCH23

 

 

 

 

Concentration in Holes per Liter Organic
III . Le Acidity SC! 80! SCI/Le
lo. Originel Original Original Organic Ratio
46 0.103 0.101 0.400 0.221 2.97
47 0.103 0.101 0.500 0.268 ' 3.14
49 0.139 0.101 0.400 0.239 2.75
51 0.103 0.050 0.400 0.202 2.48
53 0.103 0.202 0.400 0.253 4.39
54 0.103 0.504 0.400 0.306 11.4

 

I! one coeperee the dete, it will he noticed thet the die-

trihntion coefficiente ere not the eene for the eolutione ueina

eodiee thiocynnete ee they ere for the eolutione in which monie-

thiocyenete wee need, the dietributionlcoefficiente being greater

for the eolutione conteining the eodine eelt.

In ee ettempt to

expleie thie difference, which ie too lerge to he eccounted for

by hydrolyeie effecte, extractione were node in which either

mine or eodiue thiocyenete eolutione with no rere eerth

content were equilihreted with tri-n-butyl phoephete end the

dietrihntion of thiocynnete eeeeured.

“thie wee done by “ye-

in both the equeoee end the organic pheeee for thiocyenete ee

deecrihed previoue 1y.

deletion of eech were propered end ed-

jeeted to be 0.6 tor-e1 with respect to the thiocyenete. end 0.1

ml with reepeet to perohloric ecid.

Upon enelyeie. it wee

tend thet the on.“ nine wee 0.201 for-e1 iron the eel-onion

Wynne deflection. end only 0.125 foreel fro- the eodime

thioeyenete eetrectioe.

It eppeere from thoee dete. thet the

49
.eniu thiocyenete repreeeee the extrection of the rere eerthe
hy heieg estrected iteelf. In order to determine whether ladie-
thieeyenete wee being extrected, or if thiocyenic ecid wee the eein
epeeiee being eetrected, e eeriee oi eetrectione were made in which
the thiocynnete concentretioe wee veried while the hydrogen ion
eoeeeetretioe wee held eoneteet, end eleo in which the hydrogen
ion eoeoeetretion wee veried ee the thiocynnete ooncentretion wee
held eonetat. the dete for theee extrectione ere given no tehle

I", end preeented grephicelly ee tiguree 12 end 13.

tehle 3;!
lgtrggtion dete £95 MCI

 

goncentretign in undone; Liter

 

 

he see Acidity ear
[9 1 Original Originel Ozrganic‘
1 0.400 0.050 0.063
2 0.400 0.101 0.104
3 0.400 0.202 0.175
4 0.400 0.504 0.290
5 0.200 0. 101 0.003
6 '1 0.600 0.101 0.413

 

theee dete chow thet the concentretion of thiocynnete in the
ergeeie pheee increeeee rether eerkedly no the ecidity ie increeeed.
hut thet there ie only e elight increeee in the mount of thio-
eyeeete in the orgenie pheee ee the originel thiocynnete concen-
tretioe ie increeeed. theee oheervetione indicete thet the nejority
of the thiocynnete which entere the orgenic pheee doee co in the

lore e2 thiecyenio eeid, end not ee eodiue thiocynnete.

30.3 100. +I 0......ka \QDGV. \Uxth
.06 v.9 M6 N6 3
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+ N\ 0.30.5.

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Q5

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m6 MG VG M6 N6 \6

 

 

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(0.». kaCvaCOO
mt UCOXUOEL 2.3.0 00 fit:
k0 COtUEJK 0 00
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D 0.3th

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Q5
(QIuDEJO) NOS ,zo uoyoaueouoc

8

 

 

52
w 95 g-eeeodniun thiocm; to

the entrectioe o! preeeodyeiue wee etudied et different thio-
eyeeete ooeceetretione end et diiierent initiel eciditiee. Iodine
thiocyenete wee weed to edjuet the thiocyenete concentretioee to
the deeired veluee. end perchloric ecid wee need to edjuet the
initiel ecidity. the ionic etrength wee edjueted hy edding etend-
erd eodiee perchlorete oelution. the extreetioee were perioreed
ee deeerihed previouely. the dete ohteieed tor theee eetrectione
ere yreeeeted ee tehle 2'. end grephicelly ee Figuree 14 end 15.

 

 

Table £2. -;p
Mr “on $25.: is: W
#8 n e on 1e e '8
Inn Pr Adidity 808 2r tr 1
lg, ggi‘inel Originel Originei 53239;! Orgeeig
1 0.103 0.101 0.000 0.0678 0.0348 0.515
2 0.103 0.101 0.200 0.0379 0.0648 1.71
3 0.103 0.101 0.400 0.0206 0.0821 3.99
5 0.103 0.050 0.400 0.0130 0.0897 6.90
6 0.103 0.202 0.400 0.0336 0.0691 2.06
7 [0.103 0.504 0.400 0.0321 0.455

0.0706

_4_ k
w

theee dete ehow the eeee dependence on initiel thiocynnete con-
centretion end initiel ecidity ee wee oheerved for needy-ice end
leetheeue.

WMWW

the eetrection of eeneriue wee etudied in exectly the same

\ \mux.\\ \00. Wm<0 E» CDiUthmnuCOHU meCUXODIF

 

 

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k0 CO? UCJK U 0.0
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MG 0.6 MG N .Q . \6
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96 u Ecnhcmccob Rum. 0.ch
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\4 $10.00. 0%.:
k0 CO§UCDK O 00
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JUS/Q/JJQOQ uoy nqu; $70

' g, (1)

3’.
eeener ee wee the preeeodyeiue. the eolutioee to be entrected were
node to be identicel to thoee need in the preeeodyeiue extrection.
eeeept thet eeeeriue no need ineteed of preeeodyeiue. the reeulte
e2 theee extreetiene ere preeented ee teble m. end grephicel

repreeentetione of the dete ere given no tiguree 16 end 17.

 

 

35.5.1: 311
mm: 222 £21 m1:
Concentretigg in lhlee gr Lite; #
he 8. Acidity 80] Se 8. q
. 0ri inel 0r noon 1
1 0.103 0.101 0.000 0.0653 0.0374 0.573
2 0.103 0.101 0.200 0.0362 0.0665 0.84
3 0.103 0.101 0.400 0.0181 0.0846 4.67
4 0.103 0.101 0.600 0.0083 0.0944 11.37
5 0.103 0.050 0.400 0.0118 0.0909 7.70
6 0.103 0.202 0.400 0.0325 0.0702 2.16
7 0.103 0.504 0.400 0.0680 0.0347

0.510

theee dete ehow the em tendenciee ee were oheerved for the

other rere eerthe etudied.

mm it. W 9.1 mod an 19 5.29. Who-enc-

g‘ 22! gating;

In order to teet the woefulneee of the extrectioe of the rere

eerth thioeyentee into tri-e-butyl phoephete, eynthetic eixturee

e2 preeeodyeiue end eeodyeiue thiocynnetee were nede, end theee

were equi1ihreted with tri-e-butyl phoephete ee deecribed before.

leperetiee dectore were detereieed epeetrophotoeetricelly by the

eethed e! belle: eed Irentley (40).

the eeperetioe doctor ee need

 

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50
380 in Mia“ aa the ratio of nacdyniun to praaaody-iua ia the
m plan after extraction divided by tha “It ratio for tha
comm but-ca attraction. rho data from than “pain-at: are

mud aa I051. m1.

 

 

2...st . an
Extraction g; Neodmium 39$ Euaoduiufl
mut;atiog in El“ 23; Lita: Saparatiou
I“ It SON Acidity
na inal 0:1 ina Or in l‘ to:
0.075 0.02} 0.500 0.101 1.111
0.050 0.050 0.400 0.101 0.95
0.025 0.073 0.400 0.101 0.77

 

mu data indicata a variation a! ti. aaparatioa factor at
ti. ralativa amount. of diffarant rara aartha in a uixtura ma
chi-god. am though tha out-«all toacantratiou of an aartha
m but cmtant. It‘mld appur, than, that thia method

would to of doubtful valna for tha aaparatioa of a crude nixtura.

”Rams-21W

“as. tho distribution todticianta to: lanthanum, praaao-
01-1.. “pin. and airin- hava baau dataniaad. it uould ha
iutmatiu. to tan tho diattibutiau bahaviar of cm thio-
ayauata. A aolutioa’ of auoua aullata In pupa“ by raining
out: ultata uith hydtojau maxi“, and ”dia- thiocyaaata ao-o
htiou Ila ad“. I-adiataly upon the addition of thiocyanata,

a tutu-hon praipitata of talk: for-04.1 to ba autaia that tha

59
him puoxida was not the cause of the dccoupoaition of tho
thiocymts, sodium thiocyanate solution was added to an acidilisd
solutiou of hydrogen peroxide, and the solution remitted perfectly
clur. 1110 experiment with cerium was repeated with a fairly largo
mass of par-oxide prsssnt to mini-ins ths possibility of cario
cari- baiq prssut. Wha- thiocyanats was added to this solution,
tbs vol-unions prscipitats of sulfur was again vary ash in avi-
Iuos. It was concludad that ths ditticultiss in using tariuu sad
thioeyuato togsthor wars. to. great to attsnpt a study of ths carin-

attraction.

Variation! 35 £113 Absorgtion Sgctra g; 5353 tars Earth; 33

gri-n-butll ghosghato Solution!

In tho initial tosts for tho axtraotahility oi usody-iun, both
tho sguaous and ths organic phasca vars ohsarvad uith a hand spaatro~
ass”, and it was notusd that the absorption bands sssnsd to hsva
has. shiftsd. It in dooidsd that ths visibls spectra for tho
cunts phat should ha “corded and studisd uors carsfully. 8.-
plss 0! tbs mic phass vars taken, and thsir spactru- rocordsd
all. a Ischsan nodsl 0.1.4 rscording spsctmphotoutsr. Iron
thus spaatra. it as notioad that ths broad band uhich is obssrvsd
at 575 uillimicrous in aqueous solution had boon partially rsaolvsd,
sad that tha bands at 740 and 800 millislicrous had been shifted to
[coast uavslangths. Ths spectrum of neodymium .psrchlorats was

not altered to the same sxtsnt as was the spectrum of the thie:-

60
cysusts. In so attsupt to sxplain thess spsctrsl shifts. sons of
tin tri-unbutyl phosphats solution of ths parchlorsts uss plscsd
is su ovss at 110° c. to rs-ovs lost of ths uhtsr dissolvsd is
thé solvslt. Tbs spsctrul.of this drisd solution was consistsly
diffsrsst iron that of ths vat solution, and rsss-blsd uors
slossly tbs spsctrus of tbs thiocysnats solution. to ass it ths
spsstral chauass usrs psculiar to tri-u-hutyl phosphats, nsodynius
thiosysnsts crystals usrs dissolvsd in ssthanol. and ths spsctrul
of this solution rseordad. This spsctru- uss almost idantical to
that of tbs thiocysnats is ths tri-n-hutyl phosphats. It appssrs
that ths shift in spsctrsl hands in this osss is ssrsly a usssurs ‘
of ths amount of ustsr which is rmnd tron ths usodyuius. Cos-
plsts spsotra of moody-Iliu- parchlorats in tri-n-hutyl phosphats
(sot drisd). usodyuiu- thiocyanata in tri-n-butyl phosphats (not
drisd). and nsodyudun.porchlorsts in trios-hutyl phosphsts (drisd)
srs prsssntsd so Figurss 18, 19. and 20 rsspactivsly. Dstsilsd
spsotra of ouly ths rsgiou 560 . 620 sillisdcrons of nsody-iu-
psschlorats in ustsr solution, usodysiu- thiocyanats in hathsnol.

asd ths solutions dsserihsd abovs ars prassntsd ss Fizurss 21
through 15.

Ipsctrs usrs rscordsd tor prassodyuims and suariun thio-
cyausts in tri-u-hutyl phosphats, hut thsss do not show any
mrsciabls diff-arms tron that in ths aqusous phass. Thus

spsctrs ars prsssutsd as figures 26 and 27.

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Absorpfl'o'v Specrrum
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71

m Him 2! 2. m m 2: £22 22 532.2 __._£....Di-t flatten.
2g loodzgiun Thiooxonoto

no color of tho ooody-ion thiocyouto in tho tri-n-hutyl
phoophoto woo rum thou oro moody-inn oolotiono in gonorol, and
tho ohomtioo opoctm of thcoo oolutim ohowod o gonorol oh-
o‘orptioo in tho rogioo of m to 550 willinicrono. Thio io tho
mica o! ohoorptioo of tho tonic thiccyonoto cooplox. 'In ordcr
to Iota-loo whothor tho mount of iron which could produco thio
”I of obmptioo would hovo ony offoct on tho Motribution of
ooodyliu. oo oxttoction woo «do in which tho noodyniu- woo oll
oldol oo tho porchloroto, cod tho thiocyonoto woo oll oddod oo
oodioo thiooyoooto. Io thio oxtroctioc. tho tri-o-hutyl phosphoto
phooo bod tho ml color of ooodynimo oolto, ond tho choogo in
intonation coouioioot woo opproxinotoly that which woo oboorvcd
in tho loothom oolto for o chmo in ionic otroogth oquol to tho
ohoouo in iooic ottonxth h-otwoon tho neodymiu- oolutiono hoing
ooqorod. to Icko cortoic that thio woo tho only couoo for tho
(inoroooo, tho oxtrootion woo ropootod with mough fort-1c chloride
oelution oodod to Icko tho oolntion 0.90001 forul with roopoct to
1m. rho color ot tho trim-hutyl phonphoto phooo fro. thio ox-
trootion woo ouch on intonoo rod that tho oelution woo olnoot
"no. tho diotributioo oocfficiont of ooodyniuo woo conplotely
“has“. howovot.‘ It can ho “id, than, thot oncll mounts of

iron oo on inority would hovo no offset on the distribution of
ooodyoioo.

 

72

mmgmmazzfls.

1o otdor to chock tho mitotic of tho ottoct of choosing
toopoooturo co tho oxtroctioo of loothonoa thiocyoooto. ooo oxtroc-
tioo woo oodo at 33° c. tor thio oxporioont, tho oooo oelution woo
oood.oo ia too ouohor 52. tho diottihotioo cootficioot woo found
to ho 2.90. which io to ho nonporod with 2.71 to: too anchor 52.
ot 13°‘0. lhio indicotoo thot tho ostraotioo io onhonood by tho
hi‘hor tooporotuto. but not by o oisnificont ooouot. Binco tho
diotoihutioo cootficioot olplitioo coy dilforooco lo two oolotiono,
it to pothooo tattoo to'cooporo tho coocootrotioo.o£ tho lonthonmo
to tho «sonic phooo foo tho two oolutiouo. At twooty-fiwo douooo,
tho cmwtration of loothaou in tho orgonio phooo woo 0.0750, and
ot thirty-(loo cottooo. tho coooonttotioo woo 0.0769. thio lo a

dittoooooo of only 1.5 potcont.

 

 

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73

1315605810!

howiowo work on tho oiotrihutioo of an oortho hotwooo

wotu cod ooo-oowoooo oolwonto hoo all boon quolitotivo io ooturo.
to that no ottoopt woo ado to olocidato tho opocioo croooino tho
phooo bounty. or tho opocioo prooont io oithor photo. Mo io
o largo m of poooihlo opocioo proooot io ooch of tho phoooo.
thio “or bolas coooidotohly toducod to: thooo which ooy crooo
tho phooo hooodoty. hoomoo only onchouod opocioo coo ho trono-
pottod tool on photo to ooothor. Son of tho opocioo which night
to proooot 1. tho thiocyanoto not. on £86103. «my, moon)“.
I’“. oer. moo. Noam. unto)". Ignatius, otc. u poiutod
owt ot tho hozionio; o! tho oxpotinontol ooctioo. tho oxporinooto
dooorihod in thio thooio wot-o dooizncd to ohod «no light on which
of thooo opocioo woro i-portant in tho diottihutioo of tho toto
ootth thlooy-atoo hotwooo wotor ood tri-o-hotyl phooohoto. In
tho iototptototiooo which follow. Inch not roooio oooowhot
ooolitotivo. io thot oooo of tho inpattoot votiohloo of tho oyotow
oaoot ho Iooootod. lot iootoooo. tho “troo” ootol too ooocoo-
trotioo. oo ouch. ooooot ho wooowrod la oithoo phooo; ooly tho
totol ootol cooooottotioo io oooh photo ooo ho “too-nod ono-
lytioolly. ‘l'ho "boo" thiooyoooto loo coocoottotioo ooooot ho
ooaootoo oooily. olthooch a potootioootoio oothod utilizing o
oilwotcoilwor thioomto olootrodo not. would probably giwo o
hit-wolwo for thio quantity. to thio otody. howovor, tho totol

7b
thiocyanoto in oooh phooo woo estimated by prooipitation of tho
thiooyonato with oilvcr nitrate solution. With thooo li-itotiono
in Iiod, cod with tho oothod of Irving 5; 2;. (31) doocribod in
tho thooroticol aoction cox-wing no a guide, the results described

in tho oxporimentol ooction con now he discussed.

£3.55. 93 thiggzonoto Log Concentgotioo go; the. Diotrihntion
gootticiont 2g 59: taro huh;

I! tho nachonioo of tho oxtraction of tho roro oarth thio-
oyoootoo involves om typo o! oooplox hotwoon tho roro oorth ion
old tho thiocyonoto ion (owch ao K0011”, moor)“ otc.). choos-
in. tho ooooootrotioo of thiooyooato in tho oqwoooo phooo ohoold
hovo o prooowncod oftoot on tho utroctioo ooofliciont. For tho
dioooooioo of thio ottoct, lonthonuo will to prooontod ao o

typiool ”lo.

‘l’ho addition of thiocyonoto ion to tho aqnoouo oolntioo
hoforo oxtrootioo hoo o pronouncod offoct on tho ononnt of lan-
mi... which ontoro tho orgonic photo. ‘rho doto (Iohloo 1!, II.
ond n!) prooontod graphicolly in tho oxporioontol ooction (limoo
7 throooh 10) iodicoto an iocroooo in tho ononot of lonthonu
ontroctod oo tho originol thiocyonoto ion concontrotion io incrooo-
od, whilo tho ooocootrotion of lonthoooo wao hold conotont. In
ordor to troot thio ootrootion «cording to tho oothod of Irving
1; g” tho “froo” thiocynoto ion concontrotion ottor oxtraotion

io ooodod. If tho "froo" thiooyanoto ion concontrotion io ooounod

75
to ho oqwal to or proportional to the total thiocyonoto concen-
trotioo oftor oxtroction. then the variation of tho diotribotion
cootficiont‘with thiocyonato noy ho analyzed by utilizing equation

(3) £roo.tho thooroticol ooction:

10; q - A o Lou-LIE.) o (Sofia - Sinogw) +
(lo - ”1033(3) + (5060 - fifinoam).

l! tho thiocyonoto ion concentration io tho only voriohlo,
thou tho olopo of a plot of lo; q (tho diotribution coefficient)
votouo 103(505‘) would reprooont tho voluo (fiofio ~ EB), tho dif-
foronco hotwoon tho ovcrogo numbor of thiocyonoto iono oooociotod
‘with tho conplor in tho organic phooo (dono)ond tho ovorago nun-
hoo oooociotod*with tho complon in tho oquoouo phooo (as). (Noto
thot thooo oro ovorogo voluoo, ond do not nocoooorily roprooent
tho noot inportont opocioo prooont.) A logarithmic plot of this
typo io prooontod ao Figaro 28. From tho olopoo of tho linoo in
thio fisnro. tho voluo of tho quantity (505° - in) lo found to ho
two, which noono, for tho ovorogo composition, thoro oro two more
thiocyonotoo oooociotod with tho lanthonun in tho organic phase
tthon thoro woro with tho lonthonun.in tho aqueous phooo. Unleso
tho nnohor of thiooyonoto iono oooociotod with tho lonthonmn no
ono phooo to known, howovor. nothing doiinito nay ho ooid obout
tho oworoso nunhor oooociotod.with tho lanthanun in tho other
phooo. It tho volno of four for tho ovorogo nunhor of thiocyonotoo

oooociotod‘with ooch lonthonum, fig. which woo indicatod in ono

D/sfrbufion Coeffi'c/zenr

Low

 

0.9..

08-

0.7-

05—

04-

034..

02-

Ol—

 

  
   
  

/. Initial [.0 =004 F
2. Inil/b/ L0 = 0.07 F.’
3. Irma/La =0./0 E

 
 

F7'gure 28
D/sfr/bufbn of Lanfhanum
as a funcfion of
Aqueous SON Concenfrafbn

 

Log Aqueous SON Concenrraflbn

 

77
oorioo o! determinations (Table X) is assumed to be correct, then
thin treatment leads us to believe that the average composition in
tho aqueous phone is something of the nature of La(SCH)2t Other
determinations of thiocyannte to lanthanum ratios in the organic
photo (Tahlo XIII) tend to show that the ratio of four to ono
indicotod obovo woo dno oootly to coincidenco, ond thot the four
to ono rotio in the organic phoso does not nocooonrily roprocent
tho ovorngo coopooition. Fran these other data, it appears thot
tho lonthonno.in the organic phase in present on anything from
tumor to u(scm6”‘. Subtracting m thiocyonotoo fro- thooo
ovorogo opocioo in the organic phase to give tho ovorago composition
at tho oqnoouo would then imply that anything fro-.Lol” to Lo(SCI)4-
could ho tho ovcrngo composition of tho lnnthonnn.in tho oquoouo
phooo. Thin trootnent given no infonnation rolotivo to tho actual
opocico crooning tho phone boundary, but only tho ovcrogo associotion
after tho lonthnnnn.hno ontcrod tho organic photo. Tho main conclu-
sion which con be drawn io that there is oono form of thiocyonoto

complex or ion oggrcgotc proocnt in each phnoo.

Sinco some of the thiocyonute to lanthanum ratios for the
organic phnoo rcportod ohovo oro looo than thrco. it must he inpliod
thot tho pcrchloroto ion, used to control tho ionic otrcngth, io
ontoring into tho oxtroction. To loorn tho oognitndo of tho on~
troction of loothonuo porchloroto. on oxporinont voo porfornod in
wiloh.oo thiocyonoto woo prooont. Tho diotrihntion coolticioot
ohtoinoo for thio onporioont (Tohlo XI. Inn nnobor L36) woo

78
approximately 0.5. This comparatively high oxtraction cocfficiont
for lanthanum.pcrchlorata alone indicntes tho avorogo compooition
of tho specion crossing the phase boundary may be anything fro-
La(0104)3 to KLa(SCN)4, depending upon the initial conditions. Thin
extraction also indicates oithar that tho pnrchloraton of the raro
onrtha are more associated in the aqueous phone than hnn previounly
been assumed, that tho distribution coefficient of the oxtractod
npocicn is cxcoptionolly high, or that tho lanthanum porchloratc
in also almont couplotoly dinoocinted in tho tri-n-hutyl phonphnto.
Tho dintrihntion oxporinontn performed uning prancodyaiun, noo-
dylill, and nonoriuo show a similar dcpcndonco on tho initial thio-

cyonoto concontration, and thoroforo indicate niuilar concluniono.

Dependence of the Diatribution of Rare Earth Thioqganate

 

 

23 the Agpeous Rare Forth Concentration

In ordor to learn whcthor tho distribution coefficient of the
roro oarthn won a function of tho rare earth concentration, a norion
' of ouporinontn worn performed in which the raro earth concentration
who varied while the acidity and the thiocyanatc ion concentrationn
wore kept conntant. As in the previous discussion, lanthanum is

cited an a typical case.

tho loot that at oqual initial thiocyanoto ion concontrationn
th dintrilmtion of lanthanu- docroanon with incroaning lanthan-
ooooontratioo (rotrogrodo oatrootion) in ovidont (ro- tho graphical

ploooatation of tho data (liguro 15). Again, in ordor to tront

79
thio oxtroction according to the method of Irving gg‘gl, the "frco"
lolthaouo ion concontrotion in tho water phone after oxtraction io
Ioodod. If tho assumption in node that the "froo" lanthanum con-
coatrotioa in nearly oqual to or proportional to tho total oqucoua
lanthanulnaftor attraction, oquation (5) may again ho utilized. 1!
tho lanthanum nonmtration io tho only variahlo, than tho alopo of
a plot of lo; q voraua la: (La) would roproacnt tho difforcnco
(i; . i) in tho ovorazo aooociation of tho lonthanun.in tho organic
phaoo (in) and tho avoraxo aaaociation in tho aqnoouo photo (3).
such a plot io prooontod aa lizuro 29. iron thio graph, tho value
01 (I. . I) it found to ho ~5/16. which would indicato that on tho
avoraso thoro ara ono and fivo aixtoontha lanthanua ions associated
with ono anothor in tho oquoouo phaoo. Thia value for tho avorago
oooooiotion in tho aqueous phooo mount that about 48 porcont of
tho total lanthanua in tho aquoouo phaoo io proacnt aa a donor.

Tho oaiotanco of lanthanua thiocyanato in tho aquoouo phaoo aa a
“It! in o rathor nnlikoly postulato, oo anothor oxplanation woo

daairod.

Intake: (13) ha rocontly studied tho oxtraction of tolluriun
(m chlorido into bio(1~chloroothyl)othor from oquoouo hydrochloric
acid oolutiono, and chow- that the phenomenon of rotrogrodo ex-
traction my ho mlainod in another manner. Transforming his
oquotiono oo that thoy correspond to the case of lanthanum thio-
cyanoto intoad of tollurium totrachlorido, his reasoning, briefly

ototod, in ac follow.

Log D'sfr/bufion Coefficienf

 

 

 

F7'gure 29
Dis #1211 fion of Lan rhanum
as a mncfion of

A queous La Concen frar/bn
0.5 -
0.4 L
03 _

n 1 1 1 i 1

-2./ 120 -L9 -/.8 -l7 #6 -/.5

Log Aqueous La Concenrrcm'on

 

81
I! the oxtroctod species an lanthanum thiocyanato and
totratbiocyanatolanthonic acid, and tho comics acid disoociotos
in tho organic photo to torn 1.48610", tho distribution costu-
liciont, 1. io

(“(mfio * (EL-(80000 ‘ (“(WNM'N
q I s
(L01:

 

vhoro pars-than roprosont solar concontrationa. and tho sub-
ocrists o and v distinguish botoooo tho oruoio and tho oqnows
oolutions rospootivoly.‘ this oqnatioo nay bo rurittoo in tho

for.

W; . when

1 ' lpil o l1(H$Cl)o o (3’)“

(IL-(3cm). (momma

 

 

 

 

‘” ' (u). ' ‘1 ' (mnoimsclmo ’
. (3’)o(30r)o (3’)o(u(scu)6‘)o
‘3 inset}. ' ”d ‘3 " momma. '

Using tho abovo rolationships. tho conoontration of tho "troo"
hydrogon ion in tho organic phone may bo calculatod by nuns of

tho following equation:
(am ~ immune o nonmemumg“.

In tho tolluriuo oxtrootioo. lrobakor was oblo to oval-
ooto 5 Iron marl-soul roanlto, and K1 opoctrophotoootrically.
and found that by prowl: choosing tho valuos I2 and :3. ho
oool‘ (it tho snorinontol data to thooo prodictod by tho

n2
obovo oquotion quits roll. It is poosiblo that tho oxtrootions
otuoiod in this thooio could olso bo oxploinoo by a sinilor troot-
not. out tho lotorlinotioo of tho eonstont I1 is not posoiblo

{or this systo- bocauso thoro dooo not appoor to ho ony opprociohlo

diffuooco in tho opoctrol proportioo at tho too opocioo.

Of tho two nochoniols for oxploining rotrogrodo axtraotioo
of tho lanthanu- thiocyonoto, (a) tho oxistouco of o dint, sod
(b) tho ioniootiou on! dissociation of tho conplox in tho orgonic
phaso, it is folt that tho oxplo'ootioo prosontod by hrubakor is
tho loro ploooiblo of tho two onlmtiooo. 'rho dopondonco of tho
distributioo o! ooodyniun thiooyoaoto on tho initial coocoutrotioo
oi ooooyoiu- iodicoto o si-ilor conclusion in thot tho distribution

coofficiont oooroosos vith incroosiog ooody-iu- coocontrotioo.

mommggamw
ammgmmm

rho offset of o variotioo o! tho initiol ocidity o! tho oquoous
solution on tho astributiou of tho notol is ossoutislly tho sons
for loothanuo. oooOyoiuo. prosoodyoiun, one! sanction. to tho dis-
cussion which follows. loothaou- is on! os boing roprosontstivo

of tho othor raro oorths.

lsoroosing tho acidity of tho louthonua thiocyoooto solution
to bo oquilibrotoo with tri-o-butyl phosphoto docroooos tho ox-

trsctioo of tho lauthoau- ooooidorobly. ao can bo soon (to. tho

83
onto (roblo In) promtod grophioolly (Iig. ll) io tho oxpori-ootol
sootioo. I! o canto: ocid ouch os MIG!” woro tho spooios cross-
in. tho plus. boundary, it light bo woctol thot siuco thiooyonic
osid is o ooqorotiwoly strong ocid (60). tho oztrsctios of loothooun
would bo ooh-cod by tho odditioo of ooid. tho toot thot tho rovorss
of this is ooturolly tho coso “so not oocaosorily prowl thot tho
.tractoo opooiss is not a coqloa soil. howowor. u wo rocoll tho
cacti-outs). rosults on tho owtroctioo oi thiocyoooto (to. o so.
lutioo of sodium thiocyanoto os a function of tho origiool ocidity .
(toils XIV. Figuros 12' out! 13) it will bo ro-nborod that thio-
oyooic ooid moors to bo tho spocios oxtroctod. It wo codiuo
thooo tosulto with thooo of tho lonthsnuo attraction, wo my show
thot tho oxtroctioo of o col-plat ocid ouch as mutton will bo
docroosoo it ouothor strongor ocid is oxtroctoo simltoooously.

Tho rooming bohind this ugh-t is thot it tho spocioo crossing
tho phoso boundary is on coil of tho typo proposal sbowo, thou it

is tho concootrotion o! this spocios in oooh phoso which is tho
controlling isotor in thooxtrsction. If tho conplox scio coo
dissocioto into ions such as H’ sud meet)" in tho organic

phooo. thou this dissociation will roouoo tho ooucoutratioo of tho
undissociotod ELouCI)‘ in thot photo. Lihowiso, it onything woro
prosoot which hold copross this dissocistion. thoo tho ooooontrstiou
of tho undissosiotod ooid woulo bo incroosod. This roprossiou of

tho dissooiotiow o! M801). in tho orgnic phaso is just what
moors to hanou wh. thiocysoic ocid is introducoo. tho thiocyonic

osid is utrnctod into tho orgonic phoso ond undonbtodly dis-
osniotos - (st looot partially) - into hydrogon ions ond thiou»
oyonoto ions. tho inorooso in hydrogon ion concontrotion ro-
yrsosos tho isnisotion o! tho macs», which in turn prsmts
noro lonthsnnn fro- crossing tho phaso boondory. this is only
ono onlonotion of tho offset of tho acidity on tho oxtrootion
of lonthanuo, nonoly ths assumption of on scio‘conplox ss tho

inportant spocios crossing tho phoso boondory.

tho ofloot of ooidity noy olso bo onloinod by ossuning
tho ootrootoo opooios to bo tho oinplo lonthom thiooysnoto.
tho oltoot is agoin duo to tho oxtroction of tho thiocyonic ooid
into tho organio phoso. tho ontrooton thiocyonio on“ is ogoin
"so.“ to iuiso into hydrogon ions sod thiocyonoto ions, sad
it is this ionisotion which inoroooos tho oonoontration o!
”hos" thiooyonoto ions in tho organic phoso. m iooroaso in
”hos" thiocyonsto in turn roprossos any ionisotion of tho loo-
thooo. thiocyonoto. and thoroby roprossos turthor oxtroction of
tho lonthsnu tron tho oouoous phoso. thooo onlonotions of tho
oil-ct oi ooidity woro olso so“ by soloich (50o) for tho corros-
tion oi isrrio ohlorios into isopropyl othor.

tho otfoct of incroosing ocidity is octuslly twofold, no-
nattor which of tho obowo nochonis-s is corroct. tho socond
ottoct of. tho incrossing ocidity is tho r-Iovol of thiocymto

ions iron tho oquoous phoso into tho organic phaso by tho oxtroc-

85
tion o! tho thiocysnic ocid. This docrooso in oquoous thiocyonoto
conoontrotion olso cousos o doprosoion in tho mount of lonthsnun
which will cross tho phoso bonndory, and thoroby docroosos tho amount
of lonthnnwn which will onto: tho orgonio plans.

It should ho pointsd out horo thot tho largo snount of thio-
oyonio ocid which is oxtroctod is an indicotion oi ono of four
things. or o nonbinotion thoroof:

_ (1) that thiocyonic ocid is not so strong in cocoons solution
as who prowiously boliowod,

(2) thot it is o strongor ocid in tho tri-n-butyl phosphoto
thon it is in wotor,

(3) that tho portition coofficicnt for tho undissociotod
said is ontruoly high, or

(o) thot ths scid is noro strongly solvotod in tri-n-butyl
phosphoto than it is in wotor.

momma : oa_.t_i__Co-ue wtmmm
use 319.24

' In ordor to dotornino tho possiblo usofulnoss of this ontroction
prooodurs for tho ooporation oi a mixturo oi rsro oortho, tho dis-
trihntion ooofiicionts woro nsoonrod for lsnthomn, prosoodyniun,
“in... snd snorin- undor conditions so noorly idontical so it
was possiblo to noho th.. A grophicol comparison is givcn os lig—
nro 30 for tho oxtroction of tho roro onrths iron o 0A fornal thio-

oyonsts solution ond for tho ontroction tron porchloroto solution.

 

4.5 r. , ’
a. Exfmdion from 04 F SC/V , ’

Sn
1‘1
1

\

, ’ l-‘igure 30
’ DISMbur/bn of Fibre E arr/vs
, as a funcflon of
, Afomic Number

M
Q
I
\

1‘s
in
l

 

Dl'sfr/buflon OOeffiC/enr
(K

&
I

b. Extract/on 0f Perch/crates

 

 

 

0.55 - , , , ’ ’
o- ----------- /
0.5 "" ‘
l l l L L
57 58 59 50 6/

A formic Number

I7

l’ho ditforoncos botwooa sdjacont raro oartha aro not grout
tor oithor of tho conditions shown. horn is a gonoral trond,
in that tho distribution oootticionts do inerooao with ineroas-
ing atonic subor. this trond is that which would bo onpoctod
tron tho standpoint of basicitios: that is, tho lass basis tho
rat's each ion inwolwod. tho noro as would onpoet it to torn
ionic associations and thorotoro tho noro ono would aspect to bo
ontrsctod by a nonooquoous solront. no diiioroncos in tho on-
tractiou of win and sodiun thioeyanato can also bo ascribod

to basicity dilioroccos.

tines tho chango in distribution oooiiieiont as wo chango
tho raro north is snail. and sinco tho ehango in ontrsction as
tho raro oarth concentration is chongod is great, it is probablo
that this syston would not naho a satisfactory soparational pro-
ooduro. It would bo o nost dittioult tash to colonists tho dis-
tribution in a mitt-stage ontrsction prososs. bassoon tho con-
oontrstion ct tho rsro oarth. tho thiocyanato ion, and tho acidity
uuldallworyirononsstagotothanont. thoottoatoi tomor-
aturo, houowor. is suiiieintly .all that it would not to nooossary
to control tho tuporaturo vary rigidly duriu such a proooss. and
i! thorn woro a snail “not of iron introduood Iron tho ontraction
soul—t. tho anti-nation would not bo attsctod mrsoiably, as was
shownbythoonporinntonthootioctoiaanallnouatoi irouon
tho ontraotion ad noodyoi- (soo pogo 71).

corio sari. ouoos tho doooqosition o! thiooyanato, and for

this roaooo. this ayat- should bo attqtod for tho soparation
a! a ninturo only it tho najority of tho oariun prosont in tho
ninturo woro ronowod bolorohand.

s diroet coqarison of thooo ontraction data with thooo in
tho literaturo is not possiblo boeouso of tho groat variations in
ontrsctabilitios whon tho condition of tho ontrsetions aro changod.
Ioparation factors also proaont no basis for nonparison, sinco
thooo vary as tho initial ratio of can raro oarthfito anothor
warioo. 'l‘ho only consriaon which nay bo giwon is that tho dis-
tribution cooiiicionts for tho thioeyanatoa do appoar to bo groator
than thooo of tho nitrotos obtainod by rapped _o_§ g. (46).

mmnmwnmwnm
manna

As pointed out in tho oxporinontal soction (pagos 59 and 60).
deficits changoa in tho absorption opoetrun of noodyniun thin-
cyanato onist botwoon an oquooua solution and a tri-n-butyl
phosphoto solution. Only a wary slight chango wns obsorvod in
tho tri-n-butyl phosphato solution of noodyniun porchlorato iron
that in wotor. If tho spoetral ehangos doseribod in tho oat-
porinontal suction woro cauaod by tho for-notion of oono sort of
coqlon botwoon tri-n‘hutyl phosphato and tho noodyniun, it does
not soon roasonablo that tho noodyninn would bo noro availablo
(or oosploning with tri-n-butyl phosphato in tho proaoneo of

thicoyanato than in tho prosonco of porchlorato. In an attempt

89
to find a bottor oxplanation, tho porchlorato solution in
tri-n-hutyl phosphato was plaood in an cm at 110° c. to ro-
nowo as such of tho wator dissolved in tho solwont as possiblo.
and tho spoetrun oi this solution was conporod with that 5:.-
wieusly roeordod. rho ronoval of tho wator rosolwod tho ab-
sorption hand in thovro/gion at 573 nillinicrons to an ovon groat-
or ontont than that of tho thisoyonato solution. it was than
mt that tho -jor afloat in tho channos at tho absorption
ssoatt‘iothorsnsvaloiwatar ironthootnssphsrsoithouoo-
dani- ion. this renewal of wator tron tho sphoro oi influonco
oi noodyniun should bo oasior it sons notorial or ion woro alroady
prosont which had ronowod sons of tho wator of oo-ordination tron
tho noodyniun by roplaconant. moratoro. it sons that whon noo-
dyniun thiocyanato is ontraetod into tho tri-n-butyl phosphato it
has loss wator oi co-ordingation than doos tho porchlorato. rho
thiooyoooto, than, sons to hows roploeod out of tho wotos oo-
ordinatod to tho nosdyni. ions. this. than, issdditional
avid-socithoonistonoooisonossrtoiaasociationorcon-

plan botwoon tho raro sartha and tho thiocyonato ion.

‘9

 

90

(l) lanthanum noodyniun, praaoodyniun. and sonariun thio-
eyanatoo wars proparod. and thoir distribution botwoan aquoous
solutions .d tri-nnbutyl phosphors woro studiod.

(2) For such of tho four raro oartha usad, and incroaso in
tho initial thiooyanato concantration was found to incraaso tho
distribution oooiiioioat for tho sans initial acidity and natal

Motion.

(3) l‘hs distribution eooftioiant for aaeh of tho raro oortha
studiod was found to doaroaso as tho initial natal eooantratioo
no iooroaood it tho initial thiooyanato sonsootratioa and acidity
wars unintainsdmonstant.

(4) tho distribution eooificiont was found to docrsaso as
tho initial acidity woo incroasod it tho initial natal and thio.

oyansto soneontrationa woro host constant.

(5) In studying tho extraction of thiocyanato iron aquaous
sodiun thiocynnete solution into tri-n-butyl phosphata, it was

tound that thiocyanio acid was tho najor spacias antractad.

(6) Intraction of lanthonx- into tho organic phasa incroaaod
only slightly whon tho tonporaturo of tho contraction was incroascd

iron 25' 6. to 35" o.

91

(7) the distribution of noodynit- between the two phases
was tound to be unaffected by the presence of a snail anount of

iron in the solution.

(a) tor the rare earths used. the distribution oaaiiieiont
was louod to increase with atonio o‘er, or to decrease with

increasing basicity.

(9) hidoneo scans to indicate the existence of either an
lion-pair typo association or a coqlon conpound batwoon the rare

earth and thiocyanato ions in each of the two phases.

(10) Any ontraotion studios noting was o! thioeyanota would
have to be done on eariun tree rare earth solutions baaauso of
tho oxidising action of totrawalont coriun. It is doubtful that

ooriun thioeyanato nay be prepared.

9.
10.
11.
1!.

13.
1b.
15.
16.

17.

92

rnLIocum
Alders. 1.. Liquid Liquid Introction. llsorior. mtordan.
1955

Appleton. h. 3.. and Selwood. P. H. J. An. Chen. Soc. 93
. 2029 (19‘1)

Aasslin. G. l'. Separation of lore Earths by Liquid Liquid
Intraetion. Thesis. University of lllinois. (1M7)

hasslin. G. L. hdriath. I... and Coningo. I. V. J. Phys.
Chan. 25, 640 (1950)

Barnaby. O. 1.. J. Ann. Chen. Soc. ‘33.. 117A (19%)
Ianadicks. R. z. nnorg. Chan. 33. 393 (1900)
look. I. Angcw. Chen. 62A. 375 (1950)

look. 1.. and loch. E. Z. anorg. allgan. Chan. 23;,
1156 (1950)

Book. 1.. and look. I. laturwissonsehaftan go, 3“ (1949)
took. 1.. and layor. l. H. Chan. log. tech. 22. m (1953)
static. a. “Lem. 2616 (1947) ‘

hrintaingor. 11.. and latanarat. e. z. anorg. allgon. Chou.
33;. 106 (1935)

lrubakor. c. 11.. Jr.. A.I.C.U. 3121. A.l.c.0. 3179 (1953)
byrsson. 9.. and Iahlborg. V. Acts Chan. soon. 1. 1186 (1953)
Iberia, A. 1.. and lornor. II. N. Anal. Chan. 31. 1551 (1955)

lornolius. U. 0. Inorganic Synthasas ll.p. 58. lacrwaill
loch Co. lowlorh. l9“.

Iischu. IL. and heck. I. z. anorg. allgcn. Chen. 152. 146
(1962)

Pischot. V.. biota. 1L. and Jahm. 0. laturwissonschafton
25. 348 (1937)

19.

21.
22.

23.

14.
23 .

26.
27.

28.

29.

31.

32.
33.

‘93

’isohor. 17.. trance. 6.. Diets. It, 181...»... 0.. house. 0..
and lienann, l. B. Angus. Chan. 93. 317 (19511)

Fischer. 9.. and Chalybaaus. it. 2. anorg. than. 351. 79 (1967)
Fischer. 17.. and Chalybacus. I. Z. nnorg. Chan. £52. 277 (1947)
Fitch“. 9-. and fiber-nun. 0. c1... 1.1;. Inch. 3;, 29s (1951)

“.011“. we. “mt. Jo. ‘3‘ Wh’ni'ta“. no no mtxo
on... _2_5_§_. 157 (1949)

hag-ann. I. J. on. Chen. Bee. 1;. 768 (1950)

Esgiwara. t. toehnol. up“. tohokn can. 1;, 16 (1953)
(c. 1. 9;. sum

Barman. 3.. and tarsus. l. 2. tloetroehn. 55. 341 (1950)

lopkins. I. I. Chapters in the Chanistry ol the loss taniliar
llmnts. Stipes Publishing Co. Chanpalsfl. Ill. 1939

lophins. o. 3.. and Quill. 1.. 1.. rue. latl. seed. set. .12,
so (1933)

Inc. 1.. t. anorg. allgan. Chc. L61: 216 (1927)

trying. a. Quart. law. ;. zoo (1951)

Irving. l.. lossotti. I. J.. and Eunice. I. J. r. J. Chen.
“.125. 1907

Janos. c. Chan. Iowa 91. 205 (1908)

Kenneth t. 1.. and suttlo. J. t. J. In. Chan. loo. Lg. 2184
(195A) ' .

tennalloy. J. 1.. Jr. a Study of the lore tarth Acetylaeotonstas.
thesis. liehigan State University. 1956

Lerner. ll. 9.. and totrotic. G. J. Anal. Chan. go. 227 (1956)

havonthal. I. 1.. Liquid-Liquid trtraetion of lore tarths.
thesis. Univorsity at Illinois. 194.1

irah. J. I. Quart. law. _1,. 126. (19417)
hrsh. J. K. J. Chon.boc. 125 . 10“
lliller. e. c. J. Chen. toe. L931. 13107

55.
“a
57.

90

15.11». 1.. and Irantloy. .1. c. m1. on... 3;. 1433
(1950)

lioollar. t.. and Jackson. 0. I. Anal. Chen. 3;. 393
(1950)

Ioellcr. t.. and tianornen. P. A. J. Au. Chen. Boo. 1_5_.
3940 (1953) _

Iorris. .1. 1.. and Pepper. e. 1. m1. or... g. 1399 (1952)

O'Ieill. I... and hrtington. J. I. trans. loradoy too. £9.
1134 (1934)

Ioppard. I. 1.. Gray. 9. I.. and Eorkuo. I. I. J. h. Chan.
loo. 1;. 6063 (1953)

leopard. I. 1.. Ferris. J. 9.. Gray. 9. I... and hoes. 0. ll.
Jo “y.o one up 29‘ (1953)

tsppard. D. I... Asanowieh. 0.. Attorbury. I. 9.. lutqlo. 0..
M.1g'a 'o. Mm”; ‘s in. ”‘0'. ¢. 3..
”hm. 'e .o. m ”nah. Is as Jo be Oh... Me
L5,. 6576 (1953

Iadoitchiteh. a. coupe. Iondua 304.. 1169 (1911)

Iothschild. I. 9.. toqlotan. 0. 0.. and fill. I. I. J. thya.
than. 3. 1006 (1946)

Iyasrg. J. Ivonsh. r... r1411... 91. 199 (195:)

Ioldieh. J. J. thys. Chan. 69. 500 (1956)

sarhsr. r. a. omen-1o. ;. 207 (1921)

Madden. r. 11.. and 1.11.... a. s. 1.11. c1... 25. 1602 (1933)
um“... I. lhyoical 1.1. m (1906)

sahweitsor. 0. I.. and Butt. I. I. J. h. on... see. 11. 2753
(1955)

Iteinbaoh. J. 9.. and kaiser. 11. Anal. 011.. 3;. 081 (1953)
Itoinbach. J. 1.. and hoisor. ll. Anal. Chan. 33. 375 (1956)

Itoddart. c. 11.. and 11111, e. w. J. A... on... son. 13,, 11m
(1911)

Iuttla. J. I. a.a.e.r. 761 (1950)

59.
60.

61.
62.

63.

65.

71.
71.
73.

74.
75.
76.

95
50:11., J. 1'. 1.3.0.0. 2300 (1954)

8mm. 1.. and Basin“. I. 9:111. 1113:. Phys. Chen. Research
(Tokyo) 3.1. 601 (1942)

Implant. c. c. J. A... Chen. Soc. 1;. 2187 (1949)

90-31011“. 6. 6.. and M11. L. L .7. AI. Ch... 906. 1;.
3989 (1951)

1.91““. c. 6.. and 3311. I. I. J. lhyn. 011-. 55. 956
(1950)

Input». 0. 0.. and H111. l. r. J. Phys. Chan. 5;. 1441
(1967)

Tuplnton. c. 0.. and htcrson. J. A. J. An. Chan. Soc. 19.
3967 (1968)

Urban. G. 51111. too. 0111.. 3;. 347 (1896)

Urbain. 6.. and Urbain. P. Co-pt. Indus _1_7_§. 1310 (1922)
m lunch. I. A. An“. Chi. Q. 586 (1953)

van lhtuch. I. A. Man. Chan. g. 323 (1956)

wart. J. c. J. h. an... to... 1;. 3257 (1949)

Int. J. c. 6.6. 2602 (1905)

m. I. A301. 611.. 39,. £76 (1954)

Ham. 9.. hppclnn. I. A.. and To». A. c. J. Am. Chem.
Soc. 1;. 3963 (1953)

0.11.. 1. c. J. huh. nu. «1. 39,. m (1930)
Int. ‘1. 9. llama-311 33, A1 (1951)
sync, A. u. .1. Chan. Me. 1.23;. 1415

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