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146
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THS

A MAGNETOCI-IEMICAL INVESTIGATIQN
OF THE ADSQRPTIO-N' OF- PARAMAGE‘QETIC
SALTS

Tim-six 90f i'ho £23ng a? M. S.
MlCHlGAN STATE COLLEQE
Rabat? Earie Vanda: Vemw

i931

3—HE‘518

 

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'JMLIRQEARY L1

\s‘Jgr .
. i"i-"\£2‘~'"\7_l_fl 3:3].
U

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19k“

 

 

 

 

 

 

 

 

ACEEIOWLEDG‘ENT

Tho writer unhu to «pm: hi. cine-r0
hppmntion to Protector M. 1'. Rogers for his
guidunoo and helpfulness throughout the sour"
of thin work; md to the Office of Nun). Ruurch
for u grunt lab-14131215 this march.

C.‘.t.t¢.fi
0”“...
‘0‘...
an.

#0
O

A MAGNETOCHE’GICAL INVESTIGATION OF THE
ANORPTION OF PARAVAGNETIC SALTS

By

Rob-rt m1. Vander- Vanna

AN ABSTRACT

Submitted to tho School of Gndmto Stud“. of wohigm
Sinh- 6011030 of Agricultun cud Appliod Selene.
1n prbtnl fulffllnmt of the ”quit-unto
for the 405m of

EASTER OF SCIENCE
Donn-tact of anal-try

Year 1951

Appmd @@ 7/26302/3

L MAGNETOCHEMICAL INVESTIGATION OF THE
ABSORPTION O? PARAWAGHJTIC SALTS

3!
Robct Eorlo thdor Yonnn

'rho purpooo of thlo nut hoo boa to otudy tho ngnotlo mooptlbln-
tioo or «no motto iron—group alto odoorbod from oqooouo oolutlon
on Chonotl and an” sol. tanning tho mgnotlo moopbibflltioo of tho
Moos-but ond odoorboa oolt to b. oddltivo functions. from knowlodgo of
tho mount of oolt odoox‘bol tho ngnotlo mount of tho lotto: oon bo col-
onlotod. Thlo oboorvod voluo con bo mm with tho who for tho colt
in solution in orda- to «tot-duo mothor or not tho olootronlo otmcturo
of tho alt boo dungod upon mmlono

1 "do! of tho lltoroturo ohm that littlo boo boon publlohod on
this typo of 1011:. An oorly popor roportod tint tho anon-bod at“ looo
thou pangnotlon on aloud but not on onloo gol. bot tho volt norttod
rumintton.

Tho Gooy nothod for donor-data; ngnotlo ouoooitlbuttloo no and.
Thin mains muting by o bolonoo tho opporoot ohongo in night of tho
unplo tn ploood in tho ngnotto flold. Tho olootronguot oonotmotod
for this purpooo to doooribd, no oolibroflon «to for it no 517m.

Mailman” taro undo mt o tango of non otrmgtho from 8.000
to 18.600 oorotodo. Bottom oooh honour-out tho circuit In bmkm and
ottompto ndo to ouninoto roothol tma. Moorption «pennant: woro
«Mod out by odding otonhrd oolt «lotion to know: night- of driod
ohoroool on! onion sol. on! tho numb of odoorption dotominod by tho
doormo 1n oolt oontout of tho oolution.

-1-

Tho gm ouoooprtibility of puro ohoroool io found to bo -O.462 x 10"6
0.3.” nnito. cm! of oilioo 5.1 .o.511 x 10“. Magnetic ouoooptibility
voluoo dotominod for tho odoorbod poringnotio iono aro compared with tho
volooo ottoiud for tho ion: in oolution and in tho solid ototo. Thooo
romlto oro roooloulotod ond oonporod oloo in ton- ot "od'tootivo Bohr
mgnoton numboro'. Tho ion in tho odoorbod ototo oro («and to havo tho
«no ponmgnotin no thoy hon undu othor condition. coopt for on
ononoly in tho ouo of Foz(80‘)8.

In ordor to interprot thio work in tom of o nodxonion of odoorption.
o briof rovioo io givon of tho work ”ported in tho litoroturo on odoorp-
tion of olootrolytoo from oquomo oolntion on charcoal. Footoro having
tho grootoot ofl'ooto on tho nturo of odoorptlon oroc impuritioo in tho
odoorbont. ourfooo oxidoo. ohorgo or tquoouo ouoponoiono. ond ootivotion
of tho odoorhont. including both tho ootivoting otnoophoro ond tho tomporo-
taro of ootivotion. alootrolyto odoorption my bo cploinod oo duo to
'ohomiool' interootion with tho oorfooo. ond to olootroototio ottrootion
botvoon tho onrfooo Ind diooolvod ion.

Tho «ionoo proooutod points to tho oonoluoion thot. oinoo tho
pungnotiol of tho ion in oppormtly not disturbod upon odoorption. tho
ion on likoly bound by olootrootatio forooo to oxygon otomo on tho ad-
oorbont out-foo»

II

III

VI

VII

TAB L231 0F CONT SETS

DHRODUCTIONonuounu...”on..."on...”"no"...
HISTORICAL BACKGROITNDuuu.nounuuuuunun...
EXPJIRI‘FENTALouuu...annouuuo...."noun-u...
RESMSooooooooooooooooooooooooooooooooooooooooooooooo
DISCUSSIONouuu.no...“nun-noun"..."nu-u
smksmu.nouu.uu"nun-o... ooooooooooooooooooo

RBFBJRENCESOOOOOIOOO0.0.0...OOOOOOOOOODIOOOO0.000......

PAGE
1

8

4

ll
81
18
89

 

‘Jguu oval! F6 ‘4

 

LIST OF TABIES
TABLE PILGE
I FIELD STREHGTH VE‘S"’S APPLIED CUREEITo-uuuuuuuu 6
II CALIBI’AIIOE DATA AND W SUSCETIBILITY OF WATER..." 12
III ORA}! SUSCEPTIBILIIY OF FIRE CHARCOALuou...u.-.uuo 13
IV GRAY! SUSCEPTIBILITY O?" SILICA GELonunoouuunuoo 14

17 can mcmxaxmzss (110") or» mmansonam tux-
rnms AT VARIOUS “was OF APPLIED 01mm (m m-

._n ,
PEREQ)ooooooooooooootooooooooooooOoooooOoooooooooooooo 16

VI GEM! ATOMIC SUSCMIBILITIES OF PARIS GHETIC IONS
ABSORBED LED IN THE SOLID STATEooooooooooooooooooooooo 17

VII EFFECTIVE BOHR VAGNB‘TON W.5BERSoo.oooo-ononuunooo 19

INTRODUCTION

I. INTRODUCTION

In opito of tho groot inportonoo or odoorption ond ootolyoio both
in inn-try on! from o thoorotionl point of flow. vory littlo io
“tally know: about tho noturo of tho forooo mioh bind tho udoorboto
to tho odoorbont. Tho method of magnetic moooptibilitioo ha in o
for ooooo boon oppliod to thio problon. on! tho mlto oro portioulorly
otriking don tho onbotonoo odoox‘bod hoo o lot-go ponmgnotion. Tho
mo of thio invootigotion hno boon to otody tho ngnotio nooopti-
bilitioo of oono ponngnotio iron-gmup oolto odoorbod tun oquoouo
«lotion on ohoroool ond oilioo gol. It no thought thot uoing tho
mono-m odditirity low to dotornino tho mooptibillty of tho odoorboto.
ooh-thing oouhi bo loom“ obout tho typo of forooo binding tho mot-bod
out to tho odoorbont.

-lu.

HISTORICAL BACKGROUND

II o HI STORICLL BACKGROUND

Although it io gmorolly rooogniood thnt ngnotio ouoooptibility
voluoo oon bo o porori‘nl noono of dotornining tho typoo of binding
botooon otou. thio nothod boo boon ooorooly ot oll oppliod to tho
binding ixioh oxioto in odoorption. Hoot ctonoivoly otudiod {non
tho ngnotio point of vioo ooano to bo odoorbod oxygon. ixioh hoo boon
thoroughly otodiod by Jun ond hio oooooiotoo (l). Thoir rooolto ohoo
thot tho onoooptibilitioo oro not odditivo. ooonning tho ongon to bo
nolooolorly odoorbod. Thuo thoy oon dotonino tho rolotivo our» of
oxygon odoorbod nolooulorly ond of oonbinod aygon. oinoo tho lotto:
io din-gnotio. Aloo otudiod ngnotionlly oro tho odoorption or
bmnino (I). on! of oxidoo of nitrogm (8).

Coorty hoo invootigotod tho odditivity of Iotor npor on choroool
ond porooloin (o). ond boo rooohod oono intorooting oonoluoiono. Ho
fund that. ouroopt tor pulvoriood ootivotod ohoroool nnd "oloon'
porooloin. tho onoooptibility of tho odoorbod ntor no dopondont upon
tho mat of ootor odoorbod. Thin no duo proonnbly to inoomploto
dioplooonont of tho porougnotioolly odoorbod oir. Ho oloo found thot
ohon ohoroool no inoroooingly pulvoriood ond ootivotod it booono in-
oroooingly noro poungnotio. Ho uphinod thio by ooying thot tho
ohoroool Iith tho grootoot ourhoo oroo hold tho hoot odoorbod oir, ond
tho oir boing porougnotio gtvo on oboorvod porn-Ignition to tho ohmool.

8ono oork hoo boa dono on tho odoorption by porornognotio pollodiun
ootolyoto. portionlorly with rogord to ontolyot poiooning (5). Tho

ponngnotion of tho pollodinn ootolyot io found to bo rodnood npon
odoorption.

Boutorio ond Borthior invootigotod tho odditivity proportioo or
9403), ond Fuel, (6). lb.) town), ond Fool, woro odoorbod on bon-
tonito tho noooptibility of tho torrio iono oppoorod to inoroooo. Bot
non oubotonooo woro odoorbod on oolo of F403): ond of Fools. tho ono-
ooptibility no law» thon that prodiotod on tho booio of odditivity.

Solwood hoo oloo dono oonoidoroblo work on tho rolotionohip botwon
odoorption ond ngnotion (7). with portioulor Qhuio on tho oi'foot tho
ngnotion of tho odoorbont boo on odoorption.

But poi‘hnpo tho oorlioot Inn: of thio kind. ond thot rolotod out
dirootly to tho proomt invootigotion. no dono by 8. 3. Bhotnogor.

x. n. hthur. in: p. L. Kopnr (a). Thoy unlined tho odoorption rm
oolntion oi‘ iron. niokol. oobolt, ond nngonooo oolto by ohoroool on! by
oilioo gol. Thq found thot with oilioo gol tho onoooptibilitioo oro
not for tron odditivo. but with ohoroool tho ootol otono looo thoir porno
ngnotion ond booouo dimgnotio. Tho prooont invootigotion no oorriod
out oo o ohook on ond on ctonoion or thio work.

.3-

III. EXRBBI‘YFJTI‘AL

Tho ngnotio ouoooptibilitieo wore dotorminod by tho Gouy method
nioh involvoo nooouring tho opporont goin or Inn in weight of tho
oonplo won it io ploood in on inhonogonoouo ngnotio field. Tho
onount of ohongo in weight io nooourod by o bolonoo from which tho
oolplo io ouitobly ouopondod. A diogrom of tho Sony mgnotio bolonoo
nood io given in Figure l.

The olootromgnot and no oonotmctod for thio purpooe in tho
noohino ohop of tho Chniotry Deportnenrt. The polo pioooo. node of
mild otool. oro noveoble olong their cannon oxio. oo tho gop botveon
tho polo piooeo oon bo olterod oo oironmtonooo roquiro. The over-on
i'ooturoo of mgnot oonotmotion. together with rolovont dimonoiono. ore
ohm in Figure 3. Around oooh polo piooo rite o brooo epool upon
nioh io wound No. 8 D. C. C. ooppor mgnot wire. The wire io sound
in double loyero. olternoting with one-oighth inoh otripo of innlotion.
Thoro oro 30 loyofl of wire por coil with 48 tom in oooh ooil. giving
o totol of 1440 tnrno per toil. Tho totol longth of wiro io obout 7200
foot. ond the rooiotonco for both ooilo in oorioo io obont fivo ohmo.
The oeilo oon be ooolod by pumping oil through the winding» To
fooilitoto oil oironlotion olumimm 'opidero' oro loootod ot the oidoo
of tho ooilo. ond thooo opidoro oro grooved in ouoh o ny thot oil oon
love frooly fun one loyor of wire to onothor.

In order to dotornino the field otrongth produced by voriono volueo

of oppliod onrront botwoon ono ond twenty omporeo. neoourononto were

-4-

 

 

 

 

 

 

Fm. / 600V Mnawzr/c BALANCE

 

 

:0”. our F162. MAGNET CONSTRUCT/OIV
g. (left) Call and Pole
[:1 I Below) Spool and Spider

 

 

 

.Srgu POL 6 _

 

 

c' 4.

mm. ormo oro»;
.4

 

 

 

 

 

 

F/G. 3. SUSCEPT/B/L/TY TUBE

T w—m t 24!~——+z.5u \_'

7F
V 2/.0o- 3'

 

 

 

 

 

 

 

 

ndo of the mount of pull of tho field on diotillod ntor ond on o
otondord moi: oolution (29.20% NiCl2 by weight. donoity 1.8356). The
field otrength H io obtoined from tho following relotions

§(x1‘ - 1(1) sz . 5A:
were K1 . volume ouocoptibility of the liquid
X2 . voluno ouocoptibility of oir

A 3 oroo of the tube, parallel to tho polo fooeo, from
ooptulo to rotoronoo lurk; found to be 0.3224 mi.

5 g grovitotionol oonotont

A‘w . opporont (bongo in woight of flu oomplo whn plooed
in 13h. IIOMo

The rooulto obtoinod oro prooontod in Table I. and the volueo for
H1013 oro ohm grophicolly in Figure 4.

The ouoooptibility hobo no oonotructod of thin-nllod glooo. ond
no o double or coupenooted tube. with the holvoo ooparoted by o ooptun.
(See Figure 5.) Thio oonctruotion mkeo it poooiblo to ignore the mo-
coptibility of the tube; it no verified oxperimontolly that the tube
olone exerted no change in vertical force when the field no oppliod.
The upper end of the tube oonoioted of o femole ground-51o" joint.

The oorreoponding nlo Joint. which cloned off tho tube. no provided
with o loop which could bo ottochod to tho ouoponding ohoin. For oooh
Inouromont tho tubo no filled to o opecifio reference nork neor the

neck; the diotonoo from thio hark to the pole focoo woo groot mough oo

 

" x will be need in plooo of the ouotonory Greek letter to
to denote volume ouoooptibility. ond 5 in plooe of 331; to
denote noo mocoptibility.

n5-

ON

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1 8°.0x

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903158.30

TABLS I

FIELD STRENGTH“VERSUS APPLIED CURRENT

 

 

 

 

 

 

MCI Solution Wot or
Current Kw H I Zw H
fiomoreo) (gnu) A (oorotedo)_A Alp-one L.“ joorotodol __
1 fi'0o00410 B70 ~0e00030 976
8 o01600 1.738 oOOOSO 1,689
3 e03160 I,443 oOOIBO 2.390
4 e0544 3.205 oOOBIO 3.137
3 oOBOO 4,005 e00490 3.940
6 e1214 4,785 e00700 ‘.710
7 .1661 5.600 .00960 5,515
B .8111 6.310 .01245 6.390
9 .269 7.125 .01590 7.100
10 .345 8,075 eOEOBO 8,030
11 .‘00 8,695 e02330 8.600
12 .468 9.400 e03780 9,390
13 o535 10.050 e03130 9.960
1‘ .509 10.700 o03565 10.630
13 .671 11,240 .03930 11,150
16 .734 11,170 .04510 11,690
17 o793 12.220 o04680 12.170
18 o843 12,540 .04976 12.550
19 e897 13,000 .05370 12,900
30 e945 13,350 .05570 15,280

~6-

4...“

thot tho oquoro of the field otrongth ot the nrl: no negligible enamored
to the equoro of the field ot the booe. The volume of oonplo in the tube
Ioooured 7.65 cc.

The tube itoolf no ouopeudod by e brooo choin ottochod to the loft
pen of the bolonoo. In order to prevent oir cur-route from dioturbing
the oyotolo. the pole piooeo. ou'oceptibiliw tube ond ohoin were enoloood
in o oonportnont node from plywood ond pluiglooo ond fitted with o ouit-
oble door. Inoide the compel-taint end neor tho oonplo no hung o
thermometer nich permitted tonperoture molar-onto to 1 0.5 dogreoo.

The uni-micro bolonoe need no oopoble of being rood to the
hundredth of o oilligron. olthough. for the prooont work where the one-
ooptibilitioo were rothor lorgo. it no found necoooury to toko roodingo
only to the tenth of o nilligrol.

The oourco of power no o 3.0. generoter. cporoting urnlly ot 110
velto. The current delivered by the generator eould bo,voriod by noono
of o oorieo of reoiotenooo. end it woo controlled to 1 0.1 onpero. With
the lorge ourronto need. voriotiono of thio ngnitudo produced neglig-
ible field ohongo.

Suoooptibility dotorninotiono on oooh oubotonoo were nde ot 10.

1!. 14. lo. 18. md 80 onporoo. eerreoponding to o rouge in field
otrength from 8.000 to 13.600 oerotedo. In loot ooooo tn oooourooouto
were ndo ot oooh field otrongth. end the oocond monument no node
with the tube rototod through 90 or 180 degreee oo thot ony immgonoity
in the oooplo er in pooking nuld oboe up. Thio proved. however. to be

on unnecnoory proooution. Toking neoourononto over o ronge of field

-7-

otreugtho like thio oeo doubly edrentegoeuo. l) tron the oorioo of
veluoe thue obteinod. e good everege oould be teku for the ouooepti-
bility of the oubotenoog end I) thie providoo e oomeniont noeno of
dotoeting forronngnetio impuritieo.

Between oeoh menu-cunt the oirouit no broken. end en ettempt
no mode to eliminate emr reoiduel mgnotioxn in the pole pieoeo. Thio
fie done in the following manner: the current we roduood to oi: elb-
pereo. end Ihilo the direction of the current one being reportedly ro-
voreed by moeno of e reversing owitoh, the current itoolf to being
progroeoivoly out down to ion than one omporo by e carbon-pleto
reeiotor oonnectad in oorieo vith the circuit. In thio my hyotoreoio
wee Iininioed end the rooiduel field bot-moon the pole piooee no nude
negligible.

The cherooel need one Eimor end Amend C.P. Suger Cherooel. Pro-
lininry work ehoeed the presence of null enounto of forromgnetio
impurity. end eloo of en impurity which could be oxidised oith ooreto
oolution. To remove theoo, the dmerooel wee finely ground end treated
oith oonoontrutod oulfurio ecid. Although the chemo! no ouboo-
quontly nohod repeatedly with diotillezi enter, the loot trace of eoid
eeuld not be removed. Thio no not important in the ouoooptibility
meemrunonto, however, oinoe oulfurio eoid heo the some diemgnotion
eo oherooel. The denoity of tho cherooel, es peeked in the oueoepti-
bility tube, we: 0.829 t 0.004 gram per oo.

The oilioe gel nee obtained from Derioeon Chemioel Compew. It
conteinod Just e omell mount of ferromgnetio impurity. Density of

the oilioe gel one 0.800 t 0.006 gram per cc.

-8-

‘rho edoorption upwinmte were oerriod out eo follow. Ten milli-
litoro of the etenderd oelt oolutien no pipettod on to e weighed enount
(ebout own grew) of charcoal which had been prorieuely heeted et llO
degrooo for two houro to drive off uporfioiel water. The fixture no
thormghly egitetod initially end et frequent intervelo to ineuro inti-
mto mixing. After half en hour or longer the mixture Ieo filtered Iith
e ointored glue filter. end the chef-noel fleshed three or four timoe to
remove the «canoe oelt. The charcoal one thou dried for two hours et
110 dogrooo. end eftor it had cooled in e doeicoetor ito euoooptibility
no determined. The filtrate end veohingo wore enelyzod for eelt not
edoorbed. The difference botwoon the oelt content of the filtrate end
the amount of cult contained in ten millilitoro of otock oolution nee
token to be the numb edocrbod.

Anion enolyoeo wore elco run on some of the ounploo. but neithor
onion. mlfate nor chloride. ohcwed any tondoncy to be edcorbod. Fur-
ther, pH measuremento chaired tint the oolutiono become definitely more
ecidic efter edocrption had token place. At different time ettempto
were made to recover the edoorbcd salt by prolonged Inching Iith ntcr,
but in no coco no more than a. small fraction of the adsorbed oelt
roccr'ored.

Tho verioue oelt oolutiono were enalyzod by tho following methods:

1. F.3(so‘), on treated with concentrated HCl end reduced in .

oilvor roductor. Tho ferrous salt obtained no titretod with
oerio moniun eulf‘eto. noing o—phennnthroline ferrouo complex

(ran-om) to indicato on. endpoint.

-9.-

2.
3.
4.

5.

F080‘ wee titreted directly viii: corete.

Nickel weo determined grevinetrioelly eo the dinothylglyoaino.
The oobelt oelto were determined by potentiomtric titretion
with forricyanido in en emconiuxn oitreto-emeniun hydroxide
oolution (9). -

‘Janganeoo no dotormined patcntionotrically with limo” using

e neutrel pymphoephoto solution (10).

-10—

RMTS

IV. RBSUBTS

The vortioel force ecting on the ample euepended in en inhomo-
geneoue ugnetic ficld ie given by!
F 8‘§'( K1 ' I! ) H:“ e
provided one end of the angle ie in e negligible field.

:1 end I! ere the rolnne eeeeootibilitioe of the eenplo end
the arrounding tube, roepoctivoly.

H ie the neximn field otrongth to flicb the eenplo io eubjected.
A ie the crooo-eeetionel eroe of the eenplo.
If the force io neeourod by e beleneo. we have
(A! . §(K1-I' )381
3 : gmitetionel Comtem

Aw 3 epperent dungo in weight of the eenple
men pieced in the field.

nether then find the ebeoluto relno of the field etrongth B end
the eroeo-eoetionel eroe A. it io noro oonroniut to celibreto the
intro-out with e oubetenoo of tool: oueoootibility. When on. ie
done. the following reletion io obteinedo

‘3 " ‘1 “'1
O?
K .. (N.
I I

The oubeoripte l. 3. end A refer, roepoctivoly. to the celibreting oub-

etenoo. the eabotenoe dicee ouoceptibility ie being neeeurod. end eir.

-11-

The velun oueooptibility of eir (x‘) 1. o 0.030 x 10"”. but einoo.
ehon the euecoptibility cf cherooel eenplee‘eee being detorndned. not
.11 the .1.- no diepleeed. the velne need for x‘ no . 0.013 x 10".
Thio veluo wee uood einoo. in e diopleonmt neeeurnou: oith nter. it
no found thet eboet one-helf the ohercoel wolune no ei r. For oilioe
gel the K‘ correction no token to be+0.020 x 10.6.

One of the loot euiteblo eelibreting egcnto ie e oelution.of NiCl..
Th- aw- mumlblltty of 11101, 1. mum“ to wood x 10" (11).
end thie velue ie independent of ooncentretion in the neighborhood of
80% me], by weight. The oolution need no found to oonhin 89.10%
11101. by weight. to e check on the eelibretion. the neeenrnento tore
reputed ueing conductivity ntor. Fm the celibretion dete of the
MCI, eolution. the eueeeptibility nine of nter no eelculeted for
the rericue field otrengtho noeoured. The reeulto ere given in Teblo II.
It io ooeu thet the orange velue eelculetod for the ouooeotibility of
nter. -0.718 n 10"“, egrooe oetiefectcrily with the eoceptod nlue.
.0.sz x 10".

TABLE II

CALIBRATION DATA AND GRA‘J SUSCEPI‘IBILITY OF WATER

.4 Ah

mom £1.14 Strength Aw (N101!) Aw (3'0) 1:339: 10"6

 

10 8.078 4 0.330 511. -0.0198 gn. -0.724
12 9.400 .458 .0371 .722
14 10.700 .598 .0848 .718
16 11.770 -. .710 .0424 .717
18 11.540 .880 .0488 .715
to 13.850 .987 .0544 .715

 

n12-

Gree noooptibility veluee obteincd for pure cherceel ere given
in Teble III. The foot thet to veluoe obteinod ere independed of
field otrength den thet the cherooel ie free fron ferronegnetio in-
puritioe. Fro: theee neeeure-nte the gun neeeptibility of pure
ohereoel ie found o. be -o.4ee x 10".

was In
emu suscmxsxmr 0F PURE CHARCOAL (x 10"“)

 

 

 

Seaplo

Donoity A B 0 D

Alger” # 0. 835 $0."! 0.880 0.828
10 o0.465 4.468 -0.468 ~0.460
18 .461 .460 .471 .460
14 .460 .46! e438 .468
16 o‘“ .46! e471 e455
16 .464 .461 .468 .460
80 .466 .464 .460 .460

Avonge -O.46l -0.463 -O.465 41.46!

_ . . _._._..__ - A.

Theoe euplee differ ecu-enet in their hoet troetnont prior to
oueooptibility deborndntice.
A. Rooted in eir two beure et 110 dogreoo.

B. Hoetod in nouun two houre et :60 degree” noeoureeento were
node with the oenplo in e nitrogen etnoephoro.

C. Rooted in eir tn heuro et 110 degrooe.

D. Rooted in eir tn boure et 130 degroeo.

Oren neoefiibility veluee ebteined for oilice gel ere given in
Teblo IV. ill the oenploe eore hoetod et 140 dogreeo. Supleo A

through D were hoetod in eir for too hcure. mile 8 end F were heeted

n13-

three and one-hen honre in e co. etnoephere. The letter emplee ere
elight1y more Magnetic then the othere. possibly due to edeorbed 00,.
we... grew eueoeptihility ie -O.488 x 10-6. the reeulte indicate the
preemoe of e trace of fmomgnatio impurity. The ewerege obteined
from theee tenure-nee for the gm eueoeptibility of eiliee gel ie
.0417 a 10".

TABLE IV

0m suscmmxuu OF SILICA GEL (x 10“)

 

 

 

We
Demity A I O D E F

yr“ 0.90: 0.000 0.19; 0.790 0.000 mush
10 «0.897 -O.8CB 0-0.809 00.808 -O. 810 -0.811
12 .300 .809 .808 .806 .821 .814
14 .804 .811 .812 .808 .828 .884
16 .808 .818 .819 .810 .888 .880
18 .811 .819 .822 .818 .888 .884
80 .818 .818 .828 .819 .884 .886

Average no.8“ ~0.818 -°e313 «0.810 «43.826 -O.825

Ueing theee moeptihility weluee fer ehereoel end eiliee gel. we
hen preeeed t0 alouhte the neoeptibiliw of the ebeorbeli “11:. Ueing
the edditiwity reletionehipe

I

an... '3 xult” eelt * x

.durbutpuurbm
mere 1 . gren eueoaptibility
P . weight faction
we ohtein fer the ebeerred ueoefiibility of the edeorbed eelte
x . 1mm» - xedeoxteuhpedeorbent

Peelt _

«.16

-14-

The neceaeexy ante follow in Tehlee V and VI. In Table V ere given
gren eueoeptibility veluee found for mixturee of edeorbent end eelt. et
the verioue field etrengthe corresponding to the range in epplied current
from tax to twenty emperors. The average of theee nix veluee ie thet need
in eeloulating the neoeptihility of the edeorhed eelt.

Teble VI eenteine the eueoeytibility veluee found for the edeorted
ee1t ee ee1e11eted from the nation givu eheee. The eueeeptibilitiee
ere cpreeeed in term ef the native peremgnetie eonetituent 0f the
eelt. end repreeent the gun etonie eneeeptibilitiee. Sinee the non-
netellie pert of the molecule mkee no eppreeieble eontribution to the
meeptibility. theee nluee ere eeeentielly the em u the gren nole-
enler eneoeptibilitiee. except for Fe2(so4)‘. were thie eorreeponde to
one-hen the '01qu meeeptibility. Tehle V1 eleo eonteine the ene-
eeptihility veluee tieh were found to diet in the pure eelid. The
velue of MC], ie teken fro: Selmd (11), end the othere fren the wt!
of Herman (12). A 001mm ie included giving the number of nilligrue
0f perengnetie eonetituent (e.g. Ni. or Fe (111)) edeorhed per gm of
edeortnt. Alec ehewn ie the heet treetnnt given the fixturee before
eneeeptihility neeenremnte were ado, For euplee heeted in new:
theee neeenrenme were nude in e nitrogen etnoephem the othere were
expend to eir. The F.004 edeerhed en eiliee ge1 wee heeted in e etm
of co, to prevent oxidation of the eelt.

A eonrenient merieon of theoretioel with eheerred eueeeptibili-

tiee ie nede by the nee of “effective Bohr negneton mates-e” ineteed of

-15..

 

 

.... a... .3. 1:. .3. a... .2. m .. ..
3a.... .3... .26.. «an... .3... «2.... .8... 4 «o... ..
a... .8. a... .8. 2.... .8. 8.. a . ..
to... 8.6+ .85... 2...... to... .8... .8... 4 £38.... .
a... a... m... a... a... ..u. a... m . .
.8... 3.... 8a.... 8.... 8a.... 8a.... .3... 4 «a... no. .32.
a... a... 8... a... 8... .2... .2... a . ..
8.... 8...... 8...... 8.6.. 8.... .86.. 8.... 4 .08... .
.8. .8. .8. .8. H8. .8. .3. m . ..
:1... .3... .5... =1... 8...... 31... an... 4 .0... ..
3.. 8.. S». 3.. .8. on». 2». o . ..
8.. 8.. 8.. 8.. 8.. .8. . 3.. m . ..
.8... .8... «8.0.. .86. .8... 8o... 8.... 4 «a... .
.2. .3. .2. 81 21. .2. 8n. . . ..
«8.... an"... «5.... 8H..- ofiéu .8... n3... 4 .0... ..
a... 8.. w... p... 8.. .8. p... n . .
a... .8. n... a... o... .8. E... u . ..
.8. .8. .8. .8. .8. .8. .8. n .. ..
9...... «8.... «8.... «8.... 08.... 9a.... .8... q .18.... .
«8. a... «8. .8. .8. .8. .8. n . ..
.8. .8. . .8. .8. .8. .8. .8. o . ..
.3. 8n. 8.. a... a... 8.. 8.. m . .
.8... «8.0. So... .3... .36.. 2...... 9...? 4 «a... "8......
n .2 o... .u 3 3 a 3 835. .58....

38...... a: .888 mg .8

>89. .

83....» .88; a... .35... 8.8.84.5... .8 A...” .3 mmufiflmufimumfi 3m.

 

 

.16-

'l‘.’ .1: .Il‘rull 1

9i»\.ul 3.0 .- segue-v4 :9: out...“ 2.

$89.83 I...» .1 14.3.44 «33338 8:43. .4353: :3 4o Saunas .

 

 

u I I D250. Ooucoo n a t

8 5 oo: :33 m» 808. 83c. 846 4 48: ..

... .. 2.80. 3.4 n .. ..

u 3:? 280. 8.4 4 £481: ..

.. .. $48. :6 n u a
2.. 5 co: .932. a 4448. 438. 8... 4 «SE 7» 8:3

.. .. 88. 3.4 a .. ..

.. 848. 88. 5.4 4 483.. ..

.. .. 88. 2.4 n 4 .. ..

.. :80. 808. 3.4 4 88 ..

.. .. 88o. 3.4 o .. a

.. .. 88. 4n.» n .. ..

.. 2:0. 088. 04.» 4 ~38 ..

.. .. =8. 3.4 n .. ..

.34 5 no: 58.. u 88. 38. on.” 4 48:— ..

.. .. 448. 84.6 a .. u

an! 5 eons £48.. a .. 88. 436 u .. u

.. .. 88. 3.4 m a ..

.. 3:0. 38. on." 4 £48.qu .

. t g. m*.n n 3 I

.34 5 oo: .56; a .. 438. 3.4 o .. ..

58¢ 5 can... .933 u .. 458. 8.4 a .. ..
.34 5 can .932. fl. 3486 3806 3.4 4 «no: «856
«89.344 .8 is: 28m 4:84 4.9.8444 .344 .m— oaafoufi £33.44

 

 

was 958 mums an 95 @5584 whoa onfidggm ho EHBaHmHEOMB can: 56

H5. Ends

.1 7.

eneeeptibiiitiee. healing the velidity of Curie'e lee et teen temp-
ereture for theee oelte. the (receive Bohr agneben umbere ere defined

37
fl.“ 3 - g 3 2.339 1/1“:-
W
/1( eff e effective Bohr magneton number
k . Boltemenn'e eenotent
I“ . molar eueeeptibility
r - ebeolute temperature
I . tragedro'e number
15 : Bchr mgnetog. equal to 0.917 1 104° erg
eereted"

The theeretieel velue on be eelcnleted. eoouning premegnetion

ie due to epin only. from the emotion

 

/'L(eff g V/n(n+2;
here 11 3 number of unpeired electron

The effective Bohr mgneton humane obeerved for theee edoorbed
eelte ere given in Tobie VII together with the theeretieel veluee end
the experimtel veluee of other obeervore (13). 11: ie eeen thet the
veluee obteined in the preoent inreotigetion egree reeeenehly wen
’vith the theeretieel. end in needy every one an in the tense of
veluee ebeefled under other eonditione. keoptiene to thie ere Feso‘
edeerhed on eherooel end F’8(S°4)s edeorhed both on ehereoel end on
oilioe gel. The velue fer ten-em iron io too high, reeny of the

order of ferric iron. It 1o quite pouible am: the ferrous ion Ind

.18-

 

emu

 

4a.. a . m .. ..
a... a.» .. 0.. 8.. can 4 483 ..
3.4 .. . 3a m . ..
«4.. c6 .. 4..." «a.» can 4 £48de ..
#oeu e a emu n I e
2..» 4.» .. mé 2: m3 4 «SE 4.. 8:3
4a.. .. .. 8» m . .
«a.» 8.» .. «6 «a.» «on 4 48:: .
2.. .. . «on m .. ..
8.» .. . «on 4 488 .
gov t 3 Ho» 0 s I
3.0 e e no» m e e
2.4 m6 .. 4.4 3.» no» 4 48o... ..
mm.» . .. 93 m . .
on.» “a .. ad 8.. 84 4 40m: .
.3.» .. . 8» a .. .
44.. .. . «on o .. .
8.» 0.. .. 46 «mé v.8» 4 A403": .
«He» 8 c 00» a I .-
UH.» .. e 00» u c 3
mmofl .. I mm“ m 8 I
an.» «.n .. a... an.“ 93 4 «82 1.2.6
venue-3. gate-no an + av: u we .n-Ia e233 £89433
a. .\ .850 tilt. :\

 

1

 

HHb amsr

3.4m; nebuéus.” mmom MbHHDm.E

-19-

in feat been aidioed to the ferric. oinoe no preeention wee token to
protect the oelt from eir during drying of the oemlo end ouboequent
moor-onto. 1e eontreot to thie io the velue or Peso. on oiiiee gel.
were the egreeueent between the cheer-red velue for the ferrcno ion
with the theoreticel io otriking. In the letter cue the ferrouo ion
no protected fm eir by heeting under 00,. end fine aidetion wee
prorated. '

In the one of the ferric «It no aplemticn io i-edietely forth-
coming. It my be interesting here to refer egeln to the work of
Banter'io end Bethier (6). fine eloo found with ferric oelto dorietion
fron negnertic edditirity. When oubotenceo were edoorted on ferric oolo
the onoeeptibility no lowered. but dun the Foam): end Feel; were
edocrhed on butonite the euoooptibility no inereeoed. Furthernore.
Bhetneger. fithnr. end Xepur found (a) thet. elthcugh the other oelto
they edocrbed en oilice gel obeyed the edditivity rule. Fool‘ wee en

exception. eppeering to become lore perengnetic upon edoerption.

~30-

DISCUSSION

V. DISCUSSION

It is ovidont that the dots. presented chow in edoorption both on
charcoal end on oilice gel thet the paremgnotio ions do not looo their
peremgnotiom. but in the edoorbcd etete they hove eppmintely the
cone megnetie moment they here in their oelto. Thio ie control-y to the
findingo of Bhetneger. mthnr. end Fepur. whooe eboervetieno ohowed thet
ell theee peremgnetio ions heme diemgnetio when edocrhod on chereeel.
Their cherocele. hmer. edndttedly oonteined lerge mate of here-
magnetic impuritieo, which mkeo their work oomhet dubious.

It io not poooiblo new to preeent with eny orteinty e neohenion
for the edeorption. oinee little ie known ebout the not netnre of the
ohereoel ourfeoe. It ie of prime inpcrtenoe hero to knee whet rim of
onrfece catidee ere likely to be preomt on ohercoel, but thet caution
io eo yet unsettled. Beoideo. there is e greet dcel of dioagreuent
oven on fundementel ecpeoto of the edeor'ption of electrolytoo frcn
equeouo oolntiono. A brief review ie preoented here of the pertith
Ion: done on the oubject.

Although the edoorption of electrolytee by ohercoel heo been the
oubJeot of e very lerge enount of work. progreoo in developing en un-
eqoirocel theory or eeohenioe for the edoerption heo been hindered by
en ueing leek of ogre-out in the dete preoented. m. contradictory
dete oeen doe principelly to ten fectoron 1) oherocel need in any

uperinento, eopecielly in the eerlier work. ccnteined greet encunto of

.21-

impuritieo; end I) grented e pure oherooel. ito edecrbing properties
dopud very beeicelly upon the method of ectivetion. A few overdo ebont
the ctr-e ilportenoe of oeoh ct theee feotcro they be in order.

Before the 1920'e chereoelo concnly oonteined fire pereut or
more ooh. in opite of the feet thet they were emlly eeid-treeted.
i‘hio eoh oonoieted lergely of inorgonie iepcritieo ehioh oft-a reeoted
oheeicelly with the oebeteeeeo edeerbed. time the; the dete mening-
loco. And the eoid itcelf could not be completely “ed out. won with
repented extraction with water (14). Naturelly the edcozted eoid entree
lined elkeli in oolution, end beco edecrpbion no often erroneouoly
reported.

The effect of tenpereturc of eetivntion on the edoorptire pmpertieo
of cherccel heo been otudied attentively by A. King (15). Propertico
which depend upon the temporeture c! ectivetion in an oxygen etnosphere
ere. eoid edocrption, beoe edoorption. oetelytio efficiency. «tent
or hydrolytic edoorption. end the cherge end pH of equcouo ouopenoiono.
In eddition to thio. theee propertieo chenge redicelly frcn one eoti'eet-
in; gee to enother.

In gen-rel. u eppeero «mu. thet edocrpticn of eleetrolyteo fro:
equocno oclntiono can be upleined in two different aye. In the firot
piece. e oort of “chenicel' interection oen occur beteea the edocrbed
electrolyte end cone component of the edeorbent ourfece. whether thet
be come curfeoe oxide. ehenioox'oed enter repor. er the like. In the
oecond pleoe. edoorption my be duo to the ettreotion of electrostatic
chergoo on the ourfeoe of the edoorbont. A full expleneticn of edcorption

.22..

will prcbebly have to teko into eooount both of those, and possibly
other, phenomene.

The exiotenoe of ourfeoe oxideo on ectiveted dneroeel heo been
poetuleted to ohow that edeorptien of electrolytee from oelution io due
to ohenieel interectien with on eotiveted eurfeoe. T'hny inn-tighten
here interpreted their dete eo being evidmoe that ouch oxidee ere
preoent. Killer prepeoed e eechenion of edeorption bend on diooocie-
ticn end dioplnoemont of :1" end 011' ion. adsorbed by the chercoel (16).

80111101 hec proposed three specific ourfcoc oxidco. eeoh with different

propertiee, ixich ere forced et different oxygen preocnreo (1?). They

ere:
A B C
“‘5'
A :C: :C . 0 IC:
[0 I0 [0
:2 -C\ .C o 0 -C\\
O O
\o .c/ .C e 0 4-43
/ \ \
89 /o ,o
-C\ IC\ :5 e 0 -C:-0
O
/
3? 8c<0 :9 e 0 ~05
0 O

A ie ete‘ole et ell temperatures end in oxygen up to e preooure
of 8 In... end with water givee the olightly beeic group (-C-0H). 2 io
formed from 5' et 2 In. oxygen preoeure end io eteblo up to very high
preooureo. With weter it gireo otrongly beeie hydroxides. 2 io formed
from E by heeting in oxygen et 800 to 700 degreeo. end io otrcngly

eoidic in veter. King found thet oherocel expand to oxygen. eir. or

—28-

nitrio oxide produced cone oxalic acid on the carbon eurfaco (16).

He concluded that for thoroughly dzy charcoal the surface oxide io

/\C/\/\

probably 3 8 g 1 . which io the come eo Sohilow'e oxide 5.
King elec attrib/utoo the veriation in edeorptive propertiee of the char-
coelo wifi'i tenperetnre of activation to different ourfece oxidoe which
ere formed. At the activation temperature of 350 to 400 degrees an
acidic oxide io for-ed. and at 800 to 900 dogreoo e beoie oxide (19).
A maker of invoctigetoro have focal surface axideo which can be dio-
tinguiched mgncticelly (20). That oxide: do exist on the surface of
charcoal oeene «id-1t from the fact that then mygen io adsorbed on
charcoal it io not recoverable ea 08 but ea co, or CO, end that the
beet of edoorption of well amounto ioimoh greater than that of larger
enouuto. Ockront, however. hae disagreed with thio. inoioting that die
idea of eurfece oxidee io fellaciouo. that the oharcalo ere compooed
emclueively of water and carbon. Hie own exporinento and nomination
of the data of othere ohow that charcoal anelyeeo often give 0/}! oompooi-
ticn in the ratio a/i. indicating that .11 the 0 io preoent .- H30 (:1).
The other baeie theory of electrolyte edoerption from oolutien io
the oleotrochcnicel theory. developed eopecielly by 1.. mekin and hie
«worker- (23). According to them. the adsorption of electrolyteo ie
deternined by the potential at the eherooal-eolution interface. which
in turn dependo upon the preoenoe of el'?ctroohmicelly active cheni-
eorbed geoeo on the eurfaee. In effect. the charcoal eoto eo an oxygen
or e hydrogen electrode. depending upon which gee it is charged with.

If the chancel io activated with oxygen at low tmperaturee. the

~24-

oharocel bacon-ea pooitively charged in oelution and attraoto aniono. If.
on the other hand. it io treated with hydrogen. it io negative in egeouo
oolutiono. diacharging H’ iono into oolution and adocrbing catione. Add-
ing a eeall ancnnt of platiue to the charcoal anally enheneea theee
aetivitieo. ‘rhoir data indicate that. in the adoerptien of both cuticle
and eniona. there emiota a linear relation between the potential and ad-
eerption. in emlete agreeeant with thia electrochemical theory.

Difficulty in evaluating data aloe arioeo from the fact that oxygen-
aotivatod charcoal eeeeo capable of eeoueing either a pooitive or negative
charge in aqueouo eeopenoion. For couple. King found oxygen-activated
charcoal alwaye to be negative in uter (no). Veratraete found that char.
coal eoouneo a poeitive charge tea activated at 950 degreeo and negative
than activated at 460 degreee (24). Fmtin'e low-twapereture engen-
aotivated oharooelo had a paeitive charge (If). latherjee and Roychcudhcry
oaid that activated oheneelo generally have a negative charge. but become
poeitive upon ouetained weohing with conductivity water (85). All thia
enphaaioeo again the importance of activation and impuritieo in the ad-
sorption of elootrclytee.

The two theorieo of adeorption nentioned above are certainly not
mtcally eeeluoive. but probably repreeent extreme or liliting conditiona.
that io. in acne eeoee edeerption eoneiata aolely in a reaction between
the dioeelved electrolyte and the adoorbent. be it aux-face exidee. in-
organic impuritiee. or the like. And on the other hand. oonetineo adoorp-
tion eocuro merely ae the reoult of a onrfaee charge on the adeorbeut.

”cot commonly adeerptien reeulto from a ooebination of theee two d'feetoc

48-

the icne are attracted and held fact by the cppeaitely-charged out-face.
and they alao interact with the enrface by virtue of cm night he called
a chemical affinity.

In the preeent inveetigaticn it nae found that neither of the anion
need. chloride and enliate. no adecrted. Int thot after adecrpticn had
taken place the electrolyte ecluticn becane nrkedly acre acidic. Thin
eerreeponde to cationic adoorptien with dieplaceleent of hydrogen ion!
and at lent partial mtraliaation cf the eurface chargee. Thu. the
cation ie probably adecrbed by a ecrt of ion exchange proceee. in which
it ie electrcetatically bound to the nrtace.

'rhe reeulto reported in thia paper eeea to enpport the idea that
the adacrbcd ion are bound to enrface oxygen atone rather than to the
carton of the charcoal. Binding between the netallie atue need here
and carbon atone would almost certainly be of the covalent type. And
ten theee paramagnetic atone are bound to carbon atom. in nearly every
one the reenlting enbetance ie dianagnctic. or at leaet the paramgnetien
ie radically altered. 0n the other hand. the tendency for theee atone
ton linked to oxygen atone ie to torn ccnplexee which are eeeentially
ionic. and the paramgnetien ie thue untreated. On thia baeie it ie
entirely to be expected that the paramgnetien of theee ealte ehcnld be
the cane on charcoal and on ailiea gel. eince cn eilica gel the adecrbed
ealte are alncet certainly bound to oxygen atone.

Further evidnce for a notal-to-oxygen linkage ie the following.
“.cet ineetigatcra find it inpceeible to rucve the laet traces of ad-
lcrbed uygen tron charcoal. but they find that practically no adecrpticn

.26-

cccure on charcoale which have their oxygen content reduced to a very
minim by cutgaeeing eeveral houre above 1000 degreea (26).. Frumkin.
however. came to have gotta: charcoal free tron all gaeee and claile
that each charcoal adeorbee neither acide nor alkaliee (27). Therefore
’ it appoare that charcoal iteelf. that in. the pore carbon euri’ace. ie
not able to adecrb electrolytca at all. but adsorption taken placc

through the nediun of cheniacxted oxygen.

-2 7-

WHEY

VI e SWNARY

A mgnctoohemical etndy hae been made on the adeorption by cher-
ccal and eilioa gel of com pormgnetio iron-group ealta fro: aqueoue
lolution. A known amount of aalt In! adsorbed. and the mccep‘tihility
determined by the chy method. The mgnctic moment of the cdecrbed aalt
aae calculated. and. accept for an anomaly in the once of Fe3(So4)'. it
wae twnd that the ngnetie want an not altered by adecrpticn. ae
previcue worker-e have reported. Thie eeune to point to an electroetatio
type of force binding the adsorbed ealt. and the paramgnetic ion ie
probably linked to eurface oxygen atom both in the one of eilioa gel
and of charcoal.

A description ie given of the electromagnet conetmcted for theee
magnetcchenical acaenrenente. and calibration data are included. The
gram eueoeptihility of pure charcoal 1. found to be ~0.462 x 10"”. and
of eilioa gel -0.31? x 10*. A review ie given of work done on the ad~

ecrption by charcoal of electrolytee from aqneme ecluticn.

48-

hzz‘z‘mmcus

l.

3.

4.

5.

7.

9.

10.

ll.

13.
is.

14.
15.

R.

u.

R.

C.

H.

Le

P.

S.

R.

J.

P.

E.

P.

E.

A.

R3.“3§13CES
Juza and F. Omenioks z. Electrochem. 64. 145 (1950); R. Juaa.
H. iiibbe. and L. Heinlein: z. ancrg. Oren... LLB. 105 (1949).

601M“. ‘0 Ohm PhXIe. 18. ‘38 (1950)] Re Jill... He fibe.
and L. Heinlein: z. anorg. “Chem. 2_§_B. 105 (1949).

Juza and H. Tentechert: Z. ancrg. Chen., 263. 165 (1950); L. H.
Reyerecn and J. 3. mm. J. Phye. and 6311.14 Chen... L3. 334
(1949).

Courtye Cclpt. fade. £32.. 18 (1942 )3 lblde' 5&2. 7‘5 (195°)e

Pa 3153,!) Phlle "cg" 82. 131 (1916). Me Be MlkO. Do Do 3183’.
and a. a. m... 1.6;... 1.9.1. so. (1943).

Bcntarie and P. Berthieru J. lain. phye.. so. 189 um). Conpt.
read" 215. 62 (1942).

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~29:

81.
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u.
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as.
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27.

p.
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X".

A.

A.

R.

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