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ProQuest Number: 10008599

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Tho axcihaago o«to m artadlod la a owioo of aolatioao la nhioh
various mumafc of ehlorida ion m n pmmmA* Dm chlwrfcia ion mo
addad a* bydrsoblorlc aoi<S. ^nJrogas ion ooncantration oat tbs ienie
atraagth mm constant throughout ti» sasias of «part**iwt*. la ordar
80 do Pits tho mOfttrtLo «cid eoaoastration mo vorlod sli^ itty . Thin

variation w o w rw aero tban 1 *U pareaot and wo nagloctad in tbo
traataant of tbs data, too data wo aasMsrisad la Tabla TO,

h2
1.0

0 .8

0.6

•H
6
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0.2

CO
<D

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iH

0.1

0.08

0.06

O.Oh

5 .7
l / T x 105 , °K ."1
F ig u r e 6 . A rrh en iu s P l o t f o r T h a lliu m ( l) - T h a lliu m ( lI I ) Exchange
in S u lf u r ic A cid S o lu t io n .

TA&S TJX
BWHHSJSBg8 OF KCCittJtOB RAT* OR CRUKXSR COBCKHTRATIOB
m • 3 .m

( r ) * s.90 up t i( i ) • Q,ei.oo jn n(xxi) * 0.0108 g
sx*

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Uter/nole<«dn.

1
m

U
X
5
a
i
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t

0,77
0,70
0.71
0.67
0.63
0.1«1
0,33
0*1®

0*0001
0*001
0 *00%

0*003
0*005
0*000

0.010
0,015

3

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9.0
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11.0
30,0

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8,0
0.3?

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0*20
0*30
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0.0019
O.OOhO
0,0059

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QMS

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0,0023

0.030

*

Average Derletlen

0*30

A lo g p ie * o f k varan* i fW fp f yy i» Rhein to Figure 7 .

X t am be

meat th a t th e ra te f e ll m e lf a * th e concentration e f ch lo rid e ixteraaaea
■ m i tm ch lo rid e eeaeaB tratlea le eppraaclm tely equal te th e tfc a U ln *
(XXX) eonoantretlan.
t in n iw IM

The ra te then M

i l o ff m att sore ra p id ly u n til

eonoentration i» e li$ » ily aw e then tn ie e th e thalllanKXXX)

e o n s m tm tlc a ,

fit th ie range th e trend le reverend end «a inem aee la

ch lo rid e eaaeantrafclea tw inge eb n rt m inereaee la th e ra te e f «ehange
up te 0,095 £ ch lo rid e te a *

e»i nfc4«iBe prepared with chloride concentration greater than 0 . 0U5 £
ocwtetnad e precipitate end ware net exentaed ftarther,
n^yionw » | e l ,, ( 9 , 39,iiO) fhaad that ehloride inn wed cyanide ion
had ei^wtei, effects

m

tbs rate e f tide exchange la perchloric acid.

hh

1 .0 0

0 .2 0

0.10

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0.0 2

0.01

0.002

0.001
0.0 ;

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Ion.

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2 .0 0

J

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quotients (coim eotrAMett i f ^ M n s eeii*t«n ft*) fo r th e etilo rtd e mm*
p lm m t** t <*ori»g the et®dy o f th e <£ntA I t hmmm

th a t in order
A

to exp lain th e d a te , im m U m quotieiste © f the or*$«r o f 10' fo r Kx
me&a fe* ttq a ix 1^ *

A a*#thod e^Xcre^ % fM eee fo r th e cy*mide rfcudjr

(3 £ ) *e * e e e i ia ereler to detAru&m the r e tie o f th e f ir s t m l eaoend
equilibriuas q u o tie n t**

mm

tea toraatian

q u M rn m

« * larg* i t oaa ha sham tom an a

IbslsflBy®#

«*»**

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(atom ) t* toa ratio of total « M 4 i to tiaat « f to tal

t a U t a f f a ) and jr la t o n u s of «Mwnplaatoi

to to ta l

tha31ixn(X2X). I f aaa aanmm that T3S14* and T101**

&e

not m a t and

that tor v * 2 , hlffcar ooaplaKa* ax* xwt iapw taat oenaantratlwxalaa
than jr * k/k«J too** k to tha aocond ardar rato seaateoit and to is
to*

mm

oonatont ia to* obamaa of chlw ido. M ag toaatiea (19) I t

wto toon! that to* araraga of fira valaaa tor to* ratio R jjA j was
0*<® * 0,006 (oonparo with ta w ifa raluo of 0*0035), I f eao tuna tola
oalsalatod valoo, aotowa
ke

to *

hbw* wputicm tor

• 0.7? oaa bo ealoalabad and ax* listed

ia

y,

value* of

k , ««<ng

M ix VIII,

to*
tot to totototo'
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a

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fjw i or t$
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s g r w M & f& it y jia m

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0*T?
Cl*?®

0*63
®*f>6
0 *1$
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0*31
®*®n

0,?7
0.71
0.67

0 .0 0 0
0 .0 0 1
0 .0 0 2

0 ,6 2

0.003
0*005

O.Ml
0 ,2 2
0 *1 2
0 .0 1 8

0 .0 0 8

0.610
0.015

Mr
*hs oolsulstsd
tan pswoat as

wtQxm

wmpmtM

for Cl* • 0,003 $ 1* o ff by sgpradxiataly

to tbs srpsHmmML sates. A glsne* a* Flgcsra 7

Shorn that ths aspsrbm tsl sates dess not fa ll oa tbs swwbh saw s
dvaMB tiveugh the date sod tbs wars passes tiwewgb 0.S7 ter 0.003 &
efcteriids to», todleatlag tea* tbs aspsriBsntal rate* My be in « n w ,
Otherwise, tiisso date iadlest* that op to 0.00.0 g 01* ths aaewqrttons
IMNNi in ttllS

am# VAlido

the ei&e deviation o f the ©sleeleied veXne fo r 0*0X5 X ©hXoride i m
fWSm il ls

meinMm*

t wbl t ma Suwh'fttt tewirtlhiate"! « teft th flk

fNftlSiiil)®* &% thiS

awib.^Awafc a #

*

ion i^y|

{|jf

3JEX awSGMp ti^tWBiwHaWAV IwFW IW JHa S^WIT *S»**3L<$iiLti^v e

ffiffll f %| %f'y slgf IMS#
dm
fclO
ilT
»W
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t^bsi i l l s fffflfP

W^y
fteith wEIS0B3By|jW
^mttft4ti$*'ridUfc_Mftefe ‘w3mB0
IftiSftA iii A
lhfc4lL*i'^l'4i*SliekJriWm
XAA jf» erftjh
SSr ttM
«0T&
li®HWWWfflBB^Tifc/

td $ 8 # «

dfOhXOfO
eflyWRviLflW
MNfeSUEfcA.MlkJtifc;

F arebsbl^p e ith e r th e "M L * ea* th e l^ t r iw ililo r e

©f
JX
ltMfcli dW
kifeaM
fe4lW
ft4iS^mai
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( $ f b o th ) ee®$>XssK

IMF' SOSSt*
"■P^^ti^gj^

'^P

fly'

Dodson (I4O} tins

ttaei eoslM iSd isiespwis Ixi ©hXorld© oosesi*

tarettcm l*ser©*»©« the ro te o f iM e m M ^ s (in psrsltXari« eotd i» tm )
is a vsXos sereroX s r# M l o f

& m iiar the** the arsis in the

gheene* o f ohXoridSs to tn tito sM i ib s i thaXXtoa(I) chloride eespXsgss
enter ia&o His raeotXon s i His M gM f ehXsrid* ©«meeair*iiG*i» (0#$ § )*
In lig h t o f His mmtfkm nsM rs of Hi© McshMigs in
mti&m %m His tim m m o f o& toM o* i t is not
o f

tlis cSlfeurlo acid
Hast the prssonos

o^iorids lOMsilr iM o ssss ths e o s^ l^ ir of the SKShtteg* nsehani«s

«Mi s ^ a a n tits tiw tres tiain t o f the Mbs is net pos^LhXe iS tb the

infermetion iSilOh Is s^siXshle on the thsXlittw(I) end thaXXiiBa(XXX)
ehloso* eOBIiXwwwiti

U7*

vxx. m m m r m > o c m m ic m
X i has bsen found th a t th e electro n exchange ro ta tio n between
th s!X ta»(X ) sad thaXlinetfXXX) Is f ir s t «rd«r w ith respect to essh o f
th e o xidatio n sta tes o f th e element In aqueoue s a lfb rio sold so lu tio n **
ffc* ra te o f exchange was fmwsd to bo 200 tin ts th a t in poroblorio sold
so lutio ns o f coatparable to o ls strengths.

tb s dependence o f th e r a t* o f

sxohsnge so s u lfa te le a concentration lad is ate s th a t th e iaersass Ia
th s ra ts to s u lfu ric sold solutions is do* to tb s p a rtic ip a tio n is tbs
sxehange o f compls* s u lfa te spools* o f both th a lliu s i(I) and th a llls i» (X IX ).
Xhree em p irical ro ts equations m m shsiet* eaeh o f shleh sab iafS eb srily
explains th s dependence o f tb s r a t* so hydrogsn sod s u lfa te im esu>«a*
tra tio n e *

B o re r*r, i t is believed th a t th s dots are soot accurately

represented by m utation (S)#sines th is equation includes v a ria tio n s to
th s concentrations o f tb s hydrolysed sod eoiaplSK s u lfa te spselso o f both
thollissa<X) sod th alll*m (X X X )*

th e m « » l dependence o f ths ro ts in

e u lfb rie sold so lu tio n so s& taride too concentration Is q u a lita tiv e ly
explained by th e form ation o f noneaofc&nging m m * sod diohloro^caaplsKos
o f th sllio a(X X X )» and then higher chloro^QMplaxes sobering In to ths
exchange to b rin g shoot m Increase in ths rs ts a t h l$ i ch lo rid e eencen*
ir a tio n * .

Xt is believed th s t th s unusual e ffe c t th s t hydrochloric end

s n ifte r!* so ld * have on th s rs ts o f redox ro tatio n s between th a iliu s t(I)
sod th alliu m {IX X ) and other reagent* osxi be q u a lita tiv e ly explained by
th s re la tiv e m gnitude* o f th s s ta b ility constants o f th *llin m (l) and
t h s lli 3ica(XXI) eh lo rid s sod s n Ifs ts cojaplaxes*

liTb

tho s ta b ility constant fo r tho s m o c h lo ro th a llittn (I) mad mm&+
o a lf a to thal la te (I )

ham oro vary n early eq aal.

The form ation o f

th e o u lfa tto ifc a lla t*(X ) cois<pl«x upon th e ad d itio n o f s u lfu ric M id to a
hydrochloric oeM e o la tio n o f ihaliJjaa*(X) ch lo rid e weald to an explanation
fo r th e re ta rd in g o ffo o t th a t o a lfa rte oold has on the ra to o f reactio n
o f th o H ittm (I ) and eerlnK(XV)«

la th e reduction o f th o lifa a fin ) hgr

tita n la i» { III) or iro n (X I)f th e h i# s ta b ility o f tho ch lo rid e complexes
o f th a ii tBw( n*?) ao oomparod w iih the s u lfa te complex:

th e re la tiv e ly

low re a c tiv ity o f TXSX*4 sad TXCa** oombino to slow tho redaction In tho
presence o f ch lo rid e*

th e reason fo r tho fo o t ro to o f reduction in pure

• u lftr io oold eo lation s (e«g«9 when t it a n lu ^ m ) is used) ecrald ho da#
to th e form ation o f tNOOUUi*sj(IXI) s u lfa te complexes idiioh roaot ra p id ly
w ith tho rodeoing agent*

\a

CITSD
1 , S te ffe r, I . A ., 4 . fthfte. Q m , J& K m (3 9 3 *).
2*
3.

I« | «#*

AbfaWtan.

0,

309

S*t

k * Atatawfc, X * 0 *

(m b ),

|k .9 S 9 (3 9 5 2 ),
mm)

JHgftW wn, V . 0 . S .*:? . O ta , See.30to (3 9 5 3 ).

5 . Stase, f , a . u ta Bw elM ve* 0 . a * , 4 , A n, O hm . S e e .. j£ $386 (1 9 5 3 ).
4 , ftra e ta o o d , a . 4 , and M h 3 ,

a . o. ,

7* Rufaettle, 0. end Dodften, ft.

Ifa iU i.. ^

3X37 (19U 9).

sa*»# 22. ®»k* (3951).

8 , MeaemeU, H« e a t flwlrteen,, 1 ,,

4 . am.

Omm. See.

Xk

(19U9).

9 . M bM a» ft. V „ ;© $ $ *, 2 £ X7S>S (1 9 5 3 ).

30. XAMUe* ft. and ftaiaecfceg, 0 ., ft, anew*. ellsen .Chen.
33. SftgMta» a, K» wad ttaeb, ft*
IS . Stttae*. I ,, A, pfaftftlk, Jg>

8,0

l f l 37k (3927).

M dM U n 4. S el,Jg, lftlt(391*3),
(1936).

3 3 . Mftjepft. 7 .* » Itg rttk «fa«n*» A379 S3 (3 9 3 7 ).

11*. ftMWfee&Miry 0. 3 . end %p3% ft. ft*. 4. Am. <8mm. See, 2k 5773 (3958).
33. trngmm., e , s .. «*«*. awe. rar 3 (395k).
3 k . fto m o ttl, ft. 4 * G .# 4 , Xeaftg* awl M n3e«r Chen, £ 159 (1 9 5 5 ).
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