Reaction of tellurium(iv) with dithizone

f(Jund

lJ)* llilll

to

lJl* cstr:ICtctl

intO

C:lrlX~n

~l!~l~~l~~lllO~~tl~~ Or

~*lllOrOfOrlll

SOlutiOns

Of

ditilisonc (tiil~l~ol~~ltl~ioc~~lrl~ili).oIlc, H~lh). * rcyortcti tll;it tciluriuii~In 1q,50, ;\Ii\l~~‘C’lll (IV) is c~strxtcrci from rllincri~l iICi
it

c~iIllll0t

Cilsily

Iw

cstr;ic.tc*(i

cl”;“itit;lti~ol?‘. itI1

c*.StriICtiOll

‘I’llc* tiitlliaonc*

cstrac-

c.oc*ffic.ic:nt

~icl~~~ll 1,~ crstrxctcti as ‘i’o(I\‘) I:k*i(icncT \vill lxr lm~scwtc*ti llcrc tliat lx)ints to its cStrilc~ti011 as ‘i’c*(II). ‘I’llc iticrc;wirig tiiffic*ult?* in r!str;1c*tillg tclluriutll ilS its ;hS il ~~c~IlS(:(lll~~rl(~~~ of tllis ri~tiuc~tion. ilr~UCOUS c.otlc:eritr~ltior1 inc.ri!;~s;cS fiori

of

ttrliurium

(‘;irlmn carlicr”.

‘I’lltr

titration

is

tc*tr:~i:liloritic lmrit>*

of

sil\*cr

ion.

\vitll ‘I’ciluriun~

wit11

ailfur

was

from \vilS

Iiavitig

ilIlt

\vitll

ww:

tiit~lixow

ciitl~izonc free

\v;1s fr01ll

~.oiiwntratcd

lWccil>itiltc
prwipitiltc

$VtlSillXi

tllc

in

\Vi1S Ol~tiliIlC!f,l

tiiosidc

‘i‘clluriulii

\lllUSUill

as

sclcniuni

ciiositic

in

foun(i

c*SSl’lltiilll~~

from

c:OllCcntrittcd

iIl*iC.l soiuticms

clcSi~rilwt1

Of t)lC! ii\ttcr of

0 :\I Iiytirorlilc)rii: nitric:

;ls

I>!* slJ~~~~troI~i~c~tcJi~ictrii~

hy 2 l~rci*il~itiltions

I~yciroclil~Jric:

sulfur


;xirificti

()().O“;,

ilCid.

tcilUriun~(IV).

acici

ilIlt

2’l’CO:! * 1-I NO3

tile 1V;lS

from tliis solution :lIltl c:r,nk*i~rtctl to ‘I’d)= by ignition ilt -)50°. StilIl~lilrti IV) solutions \vcrc lxclxir~xi I,y tiissoivin~ ‘I’d):! in lx:r~*l~loric* acid (or trytirwllioric acid wl~cn rccluircti). Solutions of lwrclridc witi. I~ydrocliloric ikCilJll tctrilrlliorid(:. purificti I>y sllitking witlb S;ltUrilt(!ti

c~r~St;liliZctl tciluriuln(

~1llllllOl~iil

Lv;ls

tiistilictl

Sotiiiitii

iSot~wrm;iily.

io(iitic

\ViLS rtx.ryst;tilixctl

to

rcriic~w

iotlatc.

_ l

13cluai

_.__. __.

13asctl

011

the

acknowlctl~mcnt

volunics

of

;iclwous

tc*ilurium

illIt

l*ilrl)OIl tc:tracIlinricic-tiitllizonc

I). tlicsi3 of I<. ~lAlcrll!slcl:. I:lii\*crsity of ~lit~o~sc~t;~. ,\trKust. lc)fis. (;r:rtcflJl is tnaclc to Xrncrkrn (:y;tnamitl Co11l~xt11y for itI1 ;\c;t
I'll.

to 13. I. tll~l’ont ships. l * Prewlit ncltlrcn~: Cabrillo

Collcp_-.

:Il>tos.

C;llifortliit.

S~JlIlti~JlI~ 2s”.

of

‘I’ltc:

Sll;lkcI~

Iwriorl

of

ostrxction

iOIliC’

of

\v(!rC

(Jf all

litltiutli

IJ\.

IIlCi1sllrl:ll of

tlot

‘I’llc

in

iti

IJcJtll

v;ls

minute)

for

rcrrluirctl

ilitlW1

tlctcrniiticil

15

for

min

at

attilinmcnt

I>?

ccntrifu~irig.

ilt

I .l)

-11 by

fullIcrl

‘I’IIC ~ldditi~m

ilS

il

function tllC

c*ontlitions.

ilnIll)+St wt

ilIIC1

‘I’lltr

lint: IJ~!~.;IUW

\VilS

tlcternlinccl

t IIC

rcsitllic*

ill*iCl.

illitiill lxwlict

of tlicw

CssCIl-

tllc

s:ilnl)lc~

;llJS0rlJilIll*~

cut-vI* of

\V;ls

(I-ig.

sC~lllWlt~.

I)

SOtliUIll

tllC*

I)rlYl’Ill’l!

Of

tclluriutn

\\‘;\S

USr*
c)f

Ol>tiliIl

\VilS

tll(! of

cstr:ii~tal,ility ~OIl~C~lt~‘iltiO~lS il~J~~r~~SitlI;ltcl~

I ;!I

SilIlIl’,

tllc

tclluriuIii

lly

llf

tlctt!rtilill~ttioii

CU.

I>llilSC to

Ill~~il~llrC

sp:tr:ll

it

tlllm

tlCtCrIllillilti~JIlS

in

tlic

Z’,!:,.

illJSllrlJ~lIll~CS

curvc’s.


from ilIlt

Ul1OIl to

is c*orivcwicnt IllillCrill

ditllizc)nc.

IIil\‘l! acid SUCll

ostrnc*till>ilit~

for

llis

ilCitl

is given

in

pcrcliloric

sotliutn SOtlilIIll

tlctcrriiiIict1

IroIIl

tcllI~riuI~i(I\F) Of

of

\vitll

iIS tlitlli~oIIiltC

tclllIriuIii

rc!rii;iining

for

to

USC~l

Illg

IlCUtril1i~c~l

tclluriutii

tlcstrcJyin~

ilftl!f 20

of

1~;1Yllr)IltCtrill~lll0ritlC

1.5 WilS

cur\vs

\ViIS

~*~ll~~lliltCtl

of tlw

tllc!

filCtOrS

pwsenw

tl1c

\vdrC

l*Strill~tillJilit>’

tllit to

in

Xlotltrl

otlior

of tlli! :I

in

s~~~~~~tro~Jlir~tr~IIii~tl~r

il <‘i\r\’

sliravinc:

Ill~~tllO(l.

frown

StilIl(lilrtl

ioC~i
I)llilSC!

;tc*i(l

pcrl:lilorir*

I ‘I:,,

I)[;

tlll*

Dl’llc

2 str;iiKllt

slI)~lJl)~

c~ocffi~il~iits

CII.

hIotlcl

IJl!<‘illlSl!

curves

of

rcti~ovccl

of iotlicI~*.

ill)])lil!tl.

‘1‘11~: rcl~rol1~Il’il)ilit~

cOnc’c!lltri~tiOll,

of

to

off

\Vitll

lISllilll>*

\v;i3

iltl~litic~ri \VilS

c.fJrisiStStiK lIsl!t!

IJy tllct iotlirli*

O.u>,gcn

t~tXX~lllOl~itlC

fin;ill\*

illIll

I~s;lw~i;illy

CnaMc

CilrlJOIl

p11;lscs.

\\‘iIS

rlctt~I~liiiIi;~tic~ns,

iIllCIltil1

p!r tllnt

run?;.

tllct

CStrilr’tiOll

I
iIl~UCY>US

\VilS

I~crforc:

\\‘iIS

ilc.i
I)ll;lSl’ A

curves

pll;lsCS

tllc

Sulf~lric...-l,crc:lilorif.

w-w

After

iI~~ll(‘CJUS

solution

cy&!%

cloul~lc

Ii\v;\s:‘.

IIitrr~g:cw

of

in tllc witli

nlctlirJtl.

tclllIrium

,\~IB

irrtlidc:.

IIIcht

acitls

Ilyclrr~sitlc. iorlidc

\vitlI

~JfJtils~illlll

matter

SUlfiltC.

l~lr;Isc:

il~~llC’OtlS

5c*ltlorn(wc.f,untcr(*rl,

‘I’cllurirlrn

scrics

rJf

IlIll; ;I lJl;lIll c~f~rrf*~~tioA

ilCil1

orgilllic

il

(300

SrJl1itifJnS \\'zis IllIiint:iiIlc
lJ>* .IIJilSSOS

:]:{s

i1 t>*l,c*

Iwrcllloric.

its

SC~XlriltiOIl

iI1 tile

Iml~l~lirIg

;lt

if )tlirlt*.

iri

\v;Is

;~l~~~rr,.uirn;~tcl~

t~!lliIriuI~I

flI*w.rilJI!Il

ilS

~;c~lIiti~~ti

is

tl~I!ClI;Inicxlly

I)l:rl’Illoriltc~.

‘I’~~llllrillIll tiilll>’

sli;IkiIiC:

c~fluilil~rium.

Strc!nKtll

t1cr

tOget

cspxFig.

2.

REACTIOS

01:

‘I‘c(

\VITH

Ii’)

I~f-l’HI%OSE

I-,~. 2. I~x~~;I~:~;LIIII~~~ crf ‘l’~r(l\‘) c~.Iltr;‘ticJtl of clittiis~~ilc: 111 (‘(‘18; wJllltl‘~lls il. f‘Jll‘J\v*. (:I ) 2.,5“ ,’

1'.Ill

. ~.H.).I‘,

i

.\f:

I/J)

20.0

frcjn1

1.00

‘Y~ll;Lt ,‘.,‘.“I

}‘.,‘.“I..

.I/

l)crctltoric

v‘dllll~cs .

CJf

I cjl,.,‘,‘~* 1.57.1‘,

.\I: ’ .\I;

--- ._

lnlliol

Ccmc. H,Dz

(I{) (I:)

;I3

ti~iti;~l .)C,‘I

5.“0 ,‘.,I

ii fullctic~ll c)f ‘I’c ccmcviitraticms ,‘.,‘.“I..

., C,C’lO

111 , .* I,,.

1‘3

ttlc 3

iriitcat Coilof :1c,mw84 .\I:

((‘,

10.0

’ .\I.

..__..._.

in Ccl4

I:iK. .I. I~xtr;~ctitt~ility of ‘l’c(l\‘) iii (‘tI1.1. Iiiitiat ‘I’c concciitr;ttioii: v‘~llllllc.

;rclcl

pt1;1ws

Iron1 (A)

1.00 to.0

.I1 I ICI :i?r il fuiictio11 lxla.iii., 7.H.l + 10 -?I .\I;

of iiiitkl (13)

10.0

clitt1izwic ,>.,>.lll.

cc~llcclltri1tioll I’lliASC?, CClUiIl

iii

‘I’l~cbc rcl)lottctl

to

cur\*cs

ill’(! clr;t\vIi

\vlliclt ticjn

c7wffic.icnt

;ltltl

tc-lluriuln

ilt

in tllC

tllc

llcst

in


S;cc.ticm.

of tc:lluriuIii

I_:itc:r

tcrlii3

of

an

tlio

in tllis

IliltllrC!

tllc

i!s1)re.‘;sic,rl

study. of

\vlII

irc1uililx-iulrl

I~avc

\vlricli

tllc

cStrilc:tiorl

1x2 given

for tllc

c:oricctltr;iticlns

hen

reaction cstrav-

of clitllizonc

lIll;lSC.

illl\ll!OIlS

‘1‘111; Its’1

raw

c~lIlClUs~Orls

tlic

in tll(!

01:

S.\'I I'I(lC

rc1wcscnt

;irri\*c

I<,\(“I'IlJS

I~I~.\("I'IOS

5 a*c.ics in ticid srdrrliou ‘I’~*llrtrirr~~r(I I ‘) :/ ‘l’l~(* l~~~~!~l~~tllil~iltlt tc:lluriuln(I 1’) s1wl*ic:s in rniric~ral acicl soluticms is tlic (:iltiOll 'l'l!( I(( IId) ' (11'ill1 ~lll;lI~~~~~llS sl)~!c’ic!.5. ‘I’lliS c:c~ri~~l~isioli follc~\~s frorti tlic: lillC@ill. iIlc:rCilSc in tlic s~~llll)ilit\* f~f ‘I’d):: \vitll tlic* I~~*clrc~~~n-icm ~~0Ilc~c~tl’ilti~~Il in ~wrc:llloric* ;ici
(of

c2Jnst:lnt

iol,iic: .3Jrc*ugtll)

n2

0’

111~

07

to

Ic;ist

I .1f

(I;iK.

5).

(Sc:Iir~ll>rJ\ss~‘,

in

09

O?

I

;lt

.,“,_

A.. 8,

.

l-0’

sollll)iIitv fOllllC1

osicle

OhI HCIO,,

o;r M llor

Ob5 cur”.

ilc:tcl.lliitl;~tions ill-1

il]~l~lXJSiIllilt~~

u3cx1, ;is follncl

~~~lllStilllt

fOl’

0

‘.

do2

001

.

tllc’

Ob6 Al

ill

\vllic*li

lillr!ilr

I)v

067

Od6

tlic-

O.&J

iollic.

rcl;lticmSliilJ.)

~:Stl’ill~Ol~ltiOIl

irl

stwn~tli ‘l‘Ii(*

w;is

intritlsic*

5, i3 S - If>‘- ‘I .\I

I:&.

not

1.OllStilTlt,

Iii;iilltairio
sc)lul)ilit\*

of

( * 25”;:).

tlit!

‘l’lii*

tc*llutiuni

i*cl~iilil)rililil

l~C_!i\l~ti~lll

TcX):!

(solitl)

+ I.1 +. Ft ‘l’vO(OI

1) 1.

A-, =

~-l’r~o(olI)~‘~‘/~I~l ” = O._) * 10’

is

I~;lS;cd

;llltl

011

5.0

tilt!

* IO

+.qw

of

tllc.

l-l I. rcslxx*t i\*el>*.

I’rolxil~l~-

;lc’c’clllllt~ fl>l’ tllc* 50lll~‘\\‘ll;lt :\I50

fl’Oll1

tllc

.\I l-l ‘,. ‘l’llc VillUCS 0.2 * I0 -:I

lint* (.*I) 1~01110 to 0.10

* 3)Ittl)ilit\*

:I ilI'(! cll)tikillC_!ti

:I

tsIIO SlOl>l!S ~~IIil1l~iII~

Of

tllC

ionit:

lines

f1~0111 0

c.cbliilx)sitioii

lO\Vc!l* \*illUC!S ilt IiiKlior

t0

ill

0.5 tllc-

.\I

;llltl

10 1.0 XI

soliltions

l;irgcl>

;iciilitics.

[‘l’C!O(OI-1) ‘~~/(~“I’COL’.~~,,,,.~I~I~~~~ } = 0..3 * IO -:1/s * x0-” = s * IO” . Sillc*c* SCL’lllS

likely

liw

.4

in

l;ig.

5 sllo\\‘s

no


tllilt

~‘l’~~O~~‘~,~/{~~~~~O(~~l~l) “‘!:I-I’!.!}

< 0.O.j

.

Iron1

lilwarity

nc8r

0.1

.V

I-I+. it

IZecausc I-i.-,

tlic

-j‘c.”

Iligllcst

of an>* solution in ~cJIll~lilris0n of interest, tlic solul,ility

in tllc

ilcitlit~

c CiLIl I>c IlC!~lC~t~tl

L\S ;I

Illilttcr

prcscnt

cstractiun

\wJrk \vas I .\I

tu ‘I’cO(OH)+.

curve

of TcO:!

al,ovc

I .lI Iwrcliloric

acid

is gi\*cn

in I;ig. 0. ‘I’lic var>+ing ionic. strcngtli at tlic lliglicr witlitics ll~~rkcs intcrI)rct;iticm of tllc* c’oursc of tllc i’urvc UIlcTrtilill. I’ossibl>* il I)iriuClcar tdluriun~ ion is forriiccl in StrcJllg IlcrcllhJri~ ill:id. ‘I’llc Sillt 2TCO: * kI<‘lO.I, cryStallizc*tl frcmr conc+cntr:itccl prClilorir* ;ivicl solution. C’ilIl 1)1* fOrlllUlilt~Y1 ilS ;I hinuclin;ir l~Olll~~OUIl<1. O(OI~l)‘l’C.!-

0 -‘l‘c((‘lO.,)O.

I ‘r

01 0

1

2

‘I’llis ill~llC’ClllS

3

.

l’ilti0

is clifficult

tc~llllrililll

sollItioil.

clit)iizcJIlc

illlll

t0

triltc

~Ill~Orl~ilIl~C!

\vitIi

clitliizonc:

ilt

c’Urvcs

lllll

11111 ~~ll;lllc1’1’~

rcli\tivcl>’

d(JO

Illll

clt

ilIlt

illSO

;\

niiriiriluiil

;i~suillitl~ tlC!
tllilt

tllc

rcilc’tioll

in ill>SOrl)ilIlL:c

C*StrilctCXl.

‘I’llis

clos;c*r to 3.5.

tllc

Cl0 ;lt

gives

rilti0S

tll;lt

correct

ritilction lxxduc2ts ilt 020 IlIll. ditliizonc Inisturc wit11 ilIllIllOIli;l ZOlliltl_!

is

Olltilillctl.

(I>.?Scttl UllOIl

product of :ipparwtly

r\Il

IllOlCS

wliicli rcnwvctl

of tllr:

tlitllizonc

tlli!

tlitlliZolliltc

l’ilrl)Oll

ill1

t0

lllorc!

IlUt

VillUCS

Ilot

(WC*

Iiltcr),

Of tellurium)

is witli tile

formccl

;Lro

il

VillUC

:lll

in

Of

;il,Soq)tioIl wcoIld:iry

)-Jl’ilk

:lt

at

(‘II.

7il

colorctl

‘7tl

;II~Iw;ii3

clcfinitcl>* rc-ac3ioll

cl0 not ~ll*~~l!tlc~t

silllilar.

020 t0

in

CYilll I)(! lllll.

tllc

till!

Zllltl

ri\llK:o

of ;L tclluriulll

solution

contilillill~

of 0200

for

fOUlId.

(:‘I-E(J

tllccstim,?tcd

tilt’

USUilll>’

~ll~SOrl>ilIl~f2

Of

tlitliizomtc-

IllcJstl>’

Hokvcvc!r,

1)\*

Of tellurium

of tellurium

tclluriunl(IV)-clitllizonc FICncc,

rc~liltill~

3.5-.4.0,

of tllc

i!stiIll;itioll

0l)tiliIlctl

ilIllOllllt

\v;isliing

\VilS ttlUS

illisturc*

illus~ollltiotl?; Of Ix.*;Ik of

11111, l)ut

ilt

llloStl>’

13y cilrcfU1

‘i‘tN*

Iloillt

I-I~I~;z/‘l‘C(I 1’)

illlSOrl>

lie

till!

olle

\~:l\~c!l~ll~tll

rccllIirc

ilp~XY>SillliltC!

.I25

tllilll

l71tio

tllilt

Illaj~w

ill1

Of tclluriuiil

tctri1c~I1loriclc

‘1‘110

i5oSlwStic*

~lrocluc’tS

r~ai~tion

In-o(1ucts

Ilcilrly

sllakirlC:

il~~~~rlJiIl~ll

ClUc t0

Illctllotl

Marc!

I)>*

I
~‘Uri’c’S

I)?* c~stlxc~tillC:

cStl’ill’t

Krc*c*li 1~0101.. I:igurc*s

il I~ronmiS;li

l:ur\*c’s c-row ;it ;it)out

~x)illt.

for

VillllC

i+ inl~lo~~illl~~.

tctl~;l~~Illoritlc~

111Uc.lI Ulll~~~;lc~t~~lI tlitllizollc!.

ililS

:jll

11111. ‘I’li(:

525

It

C’ill’1lOll

of tclluriulii(I\‘). it1 Iii*iglit 011 r(:il(:ticJll.

little.

1J;iss CIirouc:II iIll iSoSlwstic* is fortllcvl, I,ut tllib ill)sor~~tioll

1c

~Xill’tl?‘. il

O~>tiIiIl~(l

tlcc*r(*ilSl!S

_)5”

9

1~OlltiliIl

~~rocluct?;

ini*ri~;isiiic: ;iiiiounts

020

8

0lltiIill

not

tllc* t’~il~tioIl

clitliizori~

?

to cl~~tcrilliIlc

\vliic.Il ilIS(J cloi5


c

5

HCIG,.M

tclluriuiii clitlii-

tlii:

rcxticm, ill~SOrbilIlW

% .,;

6 _

-’

z

t .

2

:;

_

*

:: 2 ‘; E c s

.e

*

.*

c

c.

2

=

3 3

-

ooco _I__

_

2. ;.

1-c; .+ .,; ; ,

n

.?

111

.1

.

.

.-I

cc3c ,,,.A&

-, 1

*1--.-t

bbOC

,

OOiTi3~ ___a..

sm..._

-1

,J-*

*

.

‘I

-,

I

REACTIOS

OF

-rc(lV)

\\‘ITH

I~ITlII%OXE

427

1.6

1.4 10 1.2

1.0

CB

.

si 08

-0.6

0.4

0.6

1X0.4 a

0.2 0.2

1.0

_____ k b I

0.6 H

0.2

-_---_.-----

‘I’fICSC!ltJ\v l.;ltilBS ;LI’C f)f~t:liIlc’cl :lt fligfl ;lifI.lcOus tclIul~iuIli ~~~t~lizl~lll! l~lJlllX’lltr~ltilJli~. l:scx:fJt f.c;Ictioli 11ot Ill*

r;IticJ. Of (‘ourSc,

lt Ilot

IJut

.).lJ,

\Vill

c.rcJe

ilt

l.lOM! lJ(’

it, :Illll

to

IllJtl’(l

525

tll;lt

‘I’lli>

iIIIi.

i’I’1* \( CSC~CY~~I~ ; I 1211z;,,, ;Illll

j.0,

of llic*

iincl

I I~I~z/‘l’~~

(.Itii*f

Iii~li II~;I\-

ijiti*ri!st

/\‘l*/(lfilIlf

lik(*I\-

tl’//llYiIll~f

l)i*

IJri*3i*Ilt

ilClll~‘ljllS its

i*ffi*(.1

i*str;ic.t

tlii5

011 I:‘.

‘I’Iii*

iii tlii*

v;iri;ilJl~~

;is

il~w~rilwcl of

IIiIlst

fri~Ii1

iii

t Iii! Of

( I~l::I~Z:,,;I l’III’\‘l‘

:\tiotlIcr

\\‘:I% lll~il\VI1,

v;ilui*.

lJr~~liiiiiIi;iI~~~

fOI’

I'lIl'\'l'S

Ki\*c* tllc*

\*;llUOS

\';lriOII?;

s;c-t of

lJIot

c’IIr\x’s

1Jf

IOg

sl10\~11

iii

c:'Il'F: IJ ._._ - --._ ._ ). r’llJ~~‘I-I&7, I, 1’1’1.I,\, ,I,

:\f)fxiri*iitlJ*

tlrib

liIic;Ir

rc;lc*tiiig

illltl lo\v

clitlIiizoIic~

I’iltiO

~Ioix3~vci~,

tlic

CillCUl~ltCtl

tlitiiizoiic

tliis

factor.

l~lottiIiC:

I;igs:

tIi;Iili*. j l-lsl)Z

.!

(il\'K.

’ I=

=

tlii-

IJcJiIits

C';III

lx~lo\v

tlI;hIl -) ilt ItiE

C0lll:~~lltri\tioll,

fiiiil

f)lot

tlii-

\v;iS

si-t

IIiiilli*

-) iIIiti;rl

Ix*

tlit-

of

\*;tlIic-s

of

IoK

I:’

(‘I’i*:,V

:lll
of

of

;llJs0rl~illl~~l~

tlii!

of IiJK

t;tkt*II

i*;i(.II

tlii<

\~;~luo of in wlric-Ii

t>*lx*

I:’

i’1’YSIf.S

fi~oiii

tllct3c

of IoK

lJlot.) yeI’i’:,,

c’ur\x*s

to

L.lJ_{)

Ii55

tli;rt

tlIi-

to

c~cjIic~critr;iticJII

froiii

I x for os;~~iilJli~s ;i

in

v;iric*il

10~: !‘I’c~,~.

fails so

,, is

Iproiti

of

r;ic.ti!tl

i:oIIiliticjII~.

IOg 1: ;lS ;I fliiil*tioii atiil

(It*+

1,st

ti~lluI~iuIIi

\‘illUC’S of IoK i I-1-1)x:,,.

I~cl;ItioIi

iii tlic

i3

iI1 ;t c~;11~lJ011 t~~tr;Ic~Iiloi~iiIc~

;iiiti

for

clitliizoIi;itc~

of

; I4~l)x

r\ I~r~litilitliir~~

IWi3~lllcS error

I)c~.;~tiw

Ilcvx* c2rl)ori

tolliIriuIII

c~;rlc~ul;Itcil

:~l-I)z~,,

I0 :,,.

S.

a sIIi;ill~r

of tlIc: ~Ill~il-

(0,

c~sl~i:I~itIic~Iit;il

tlitliizimi~

~~oIIsi~tiII~

I:iK.

c~oIi~~cIrtI~;itioIis,

;~ri;ilytic:;il

of

tlic \~Iic*rr

ratios

sfx*c.ific.

(Sw

\v;is

( c>llt, tllc*

So

IlIC: I:’ \Vl!I’C’ t~ll<~‘ll fl’lrlll tllC*St*_1 (‘llr\‘i3 for

\vitli

;LY ;I

lali;Iw

ilitliizcJIIi*).

cxjIi~t;~nt

10~:

:liicl

:

i~oIic~oIitratioIi

of

2.5

furtlic*r.

w~l\‘i*tit

l~0ll~~l~lItl~ilti0ll

sc*c*tioIi.

~*;ilII~~s

Of

~~~Jll~~~lltr~lt~fjIlS

;I$ tlIi* r:Itio

orK;liiic.

uiitlcr

rc;Ic~tioII

ilo

~~ol~~.l’~r~Y~tfill)~

of tlitl~izoiii:

itIiti;ll tllc*

I )f j ‘I’l’ :\y ;I t trilc~ilil~riutI1

‘7’i~I,c i:, tlic! cvliiilil~riuiii

frim

it5

7’1,

iii \vliii.Ii

tc:lluriuIIi.

c~cluililJririII1 111: I;c*lJt

lJrc~~*ioIis

ciluililwiiirii

of

c.olic.i!tltr;itic)li

u?;iIIc:

\\‘(‘I’(’ llS(‘l1. VilltlCS

\‘illlll’S

tlii*

i:cluililwiurii i,*

lJrilil1li.t

of

Illil?’

7f’,

I:ltilJs IiJ\v

iIi\*~*~ti~;itc~iI

dithiztlm

iillltiis~.il)lc*

7lJ,

ilitlii~cm;it~t.

IicJt

is tl~*fiiic:il

~~~lIIililJI~iriIII

;iIJ-i*IIi*c

iis tlic

ratio

5\‘stcllls

\Vitli

iJiIt\~i*i~ll3

(I Ilit

ITip.

r~~~ll’til~ll

;iIiotlicr \V;IS

l~ilrlJ0ll tc,tI.;ii-liloI~iil~~

tllc

fiiIic~ticJIi

t1~ll1IriuIII

fuii(:tic8ii

;I

IOK

ii

\\‘;I?; c~;Ili~Ill;itctl

curv(*s tllilt

is

lJllLl?;C.

t-str;ic.ti*il as

I:‘

iii

o.si~l;itic~II

iill

in

;\lJlJ;iI~cIItI~~,

ti~lliII~iil1Ii

tll(*

;ii:tu:il

rcprc:wntiIiC:

Ki\‘illF:

rlllh

17Jl~f~ic’il’ll!

iii

aciwfdcrl

tlic

tllosc

tliosc

clitliixi~Iic~

/:‘. of

of tc+II~irilltii

unlike

T;l,

tclluI~iutII,

iii \vliicI1

l’.\fY(~l’/ill~I

I)>* ~~;~I~l~oIi tc:tI~;Ii~l~l~~I~icl~~ SiIicx*

I'ig.

t\V(J

of

ib oci*urrin~,

l~lJll~t~lllt.

l>o.~silJilit\*

iIl~tll!~~lls ~)ll~lSic~~;lt

;iliCl

will

r;itiiJIis

c~oc~ffir~ic*IIt,

;I l’ll~lilt~~ of

;is

iii

~~~l”:~~i;Ill~~,

f01~111~~~1. ‘I’liis

!*tic.;Il c.olll.c’iltt.;~til,ii~

l’~~lliII~iIiIIi

anil,

c~cJIicwit Ix-

i~sLI~;~c~ticJII

Ii~ti~;ic~liloriilc)

llClX!ss~lril~’

C'iin'c'S

4 tii;i>* ix

i:oii~l~in~itio~~,

III i:Llr\‘c*s iiii~liiilcs

Iii*< iri 5;\3ti:riis

f~c’h~‘l*lt

‘I’lic:

INJt

till+

wt

tlris

011c reaction

;I SOlIlC!\VIIiLt IO\\’ \*;I~II(: of j.(N).

;iiic)tlir*r

ilitllizc)iicr

I.;1ti0

\vitll tlI;Ill

if iiiori!

l:~Jllc~1ltr~ltilJliS ;iilil tfic IO\\‘eSt

10~:

(l4:!l)z],,

lIl’\‘iiLti0lls

ilctcriliiii;ltii,ii

I>Ccv~lllcs

IiIrgl!

=

-4.2.

:\S

;li~lli~o~ls ti:lluritiIli ril;i!* of

1x2 c.slwi.ti*il

tclluriuIii,

Iicnrc*. anil

soliic

and

iIll_ciltly

~x~iiitcil

c.ollcl~llt~iltil~llS in tliis tlicrcwitli

Ull~crtililltV

region. tlic

;iriw.s

I~EhCTIOS

01;

‘I‘C(

Iv)

\VI’I’H

429

DITHIZOSI~

00

IL-//c*Ct(Jf /I_\7 iY rJ,
tlIc 1:

5trcnC:tII

ionic-

carl~orl

tctracl110ritlc*

;IS ;I futlcticm

kq,t cx~Ilst~lIlt) i tlJIz;,, a1111 l~c~r1~11loric~

rcIluc.tions

of

of

tllc

so tliat 1-I-l’:,,.

I .0 .\I,

tl1;lt

on

tt,l,Z

111,1~1.1~,.I’l’Cl\~

;lIltl

ilt 2.h)

ilcitl

lwr~liloric initi;ll

;tloIlc*.

c!cluililwiuIil

* IO-:’

.V

wnawtr;~tiori

i.o~ii.cIitr’~Ition l)lli1S;(‘.

in tlli* il(1\lL!O”S

1~01~1’~I~triltioII

csistinc:

tlic- IxIsis

3logfJ

(--c?log:TI.[.+ ;)

tllc

tlIc! Silnlc’

tdluriurii

I

-1.!* -H -08 Log HClO,-molarlly

of Icflrrrirrm of

tlic* I:“?; for (Tur\*c :1 in l;ig. ;j

IlilIllC’l>*

ni~icl~

alltl

1)ll;lw

li~*~lrcJ~cII-ion

wit1 (z.(j.+ * 10 ” .\f wcw

witlI

L

11:ivc in ‘1’12

tlrc

otlwr

Ixxn tllc

of 13Llt

CStrilctioIl

;iclut2ous

il

ill

\\‘c rccluirc

\*ilriill~kS

rcxlwctl

in tlic

;lt

tlitliizonc

to

tllo

flX)Ill

pli;Iw).

Iwing satnc I.<)

XI

‘l’llc

IIf tlI<* rcl~itiomliilx

= - 0.45

Curves N all<1 C in Fig. 3 llil\‘C not rcprcscnt systcnls wit11 sufficiently in the rxngc trcntcd in this ppcr.

lm2tl rctluccd lwcaus;c it is not ccrtnin tlwt tllc) IiiKll c
.-I Jld.

C/l

irrr . .afclt1. 38 (1007) .lrl-434

J
bl!tl~VOl

c:011st;111t

v;~lucs I)OirltS

lellrrrirrirl rstrucfion

1;ig

IO,

COllStilIlt

cclUilil)riulll

c.ovcrinC:

tllc

Strili~llt

0Jcffiicictrt

urrti crr/trcc~lis tcllzfriuru

coucerltrdiou

1xr~IIloric acid at S and tllus rcprcsents avcragwl ‘I’lliS ],l’Jt iS ckrik’c!(l frOIl1 I’iK. [ H~lh!,,. -_3.2. ‘I’IIc l)cst straigllt lint! tllrougII tllc in tllc r;lngc 10~ ! I I,lI;zj,, = -4.2 to Iti ;ilC for a IIZLS il SlOlM! Of -0.45.

In

lCJf_f I:’

is

plotkd

clitllizrjnc:

~IJqlillst

cc~nc~crittxtion

log

of

(‘l’cjtr

O.:j

rrttig:ct 10~ !'I'c*& = -0 to - 4.4 ; tllcsc rcpwscmts liiw of slf)JW - 0.47 sittisf;tc:toril>* I Io111~*il sitiglc! c:xtrac.tion Wilc’tilJIl is owurrin~,

in

* 10-d KdUCS

x .o

rl2

;V

(log

ilrC

iH2I>xi,,

J)lOttWl

=

in I;&.

-3.2). I I.

A

t Ile lxjints. it S(fcllls

jUstiliill>lc

to ~~ollClUtl~!

1.0

0.0

grccri Ci\rlIOIl tctracliloriclc of c:.Vlrccc*ls. \\‘llcn ;I lm)wnislI clitliizonatc! :knti tlitliizonc is carefully Iili.sc~tl wit11 clilutc i~llllll0lli~l funnel Ilolclin~ tllc t\vO I>llilSCS, tllC iis I,>? slo\vly inw2rting ;I wparntor~ (ch’.. 2 IV), Furtlwr mising results carhn tctracliloritlc Iwc:olnc:s 0rilll~C alter i\ few inb2rsicms;. illltl tllc! c’ilrlX)ll tctri~cllloriclc l>llZWC in tllc clcconl~~~~sitior~ of tclluriunl tlitlli;?cJlli~tc, .-;irr,rlorlicc 7iY~SIIiItg

cstract

:I IJd.

of

Chiw.

tclluriuiil

Actrr.

.$H (I’J07)

.) .! I -.,,{.)

‘I’l~c ratio lC! riltios, r;iIiginC: from I .(I5 to .+.7, \vcrc Ol)ti1ilIC!(l.

10

08 0

06

I

9 04 02

ITronl Iiltcr)

Ill;ly

IN

I:ig. 12, F of tc:lluriurii t:5titti;rtccl il5 rou~lily

11111. Alw)rlmnccs

\vcrc

CStl-il~)OliltCtl

tlic effect of tlic cl(!c.c~nil)ositioll Solid rcticliorr ~r0drfcl.s.

ClitlliZOIliIt~

.JO,OOO at to zcrr)

tl1c

titIic*

(tlloUg~lt pe;Ik

aftr*r

of tllc solution. ;\ttc!nlpts bvc*rc* m;ltlrt

to

lw

nc’;ir .+50 illIlIlI(~Ili;L

;1S sllO\Vn

\vilSllill~

to

020

minimize

tclluriunl in sodium IiylilC’k l>rwipit;Itc \VilS Ol>ti~iIlC!Cl, wllicli \VilS \v:NllC!tl witli 3 Xf Ilytlrochloric acid i\nd clricd ut room tCrlllXXltUrC. ‘I‘llis solid clissolvccl rc:ittlil y in chloroform (ICSS c;lsilv in cilrI)otl tctr;~cllloridc) to Rive iI ycllo\v-bro\~I solution, <:lli\IlKiIIg rlUickly in color to grccnisll h-own. It dissolvctl in ilI)SOlUtC ~!tlIi~nOl. KivinC: il stnblc brownisll YC~~OW :mluticm. ‘I’lIis solution s~Io\\‘c(~ il single iIbs~rl~i~ncc l>ciIk at 430 ntI1; little or \ViLS ;ipproxima?tcly no fret clithixonc was prcscnt. (: i\t 440 nni, ~)iLSl!Cl on tclluriurn. Cl. ‘I’hc prduct is 8 rnisturc, and 25,000. ‘I‘)lC solid conti~incd IO.<)‘::, ‘I’c alIt X2.4”{,

clitlli~OniltC

I>y

;lclcliIig

:1

Inisturc

of

I)Otil5SiUIll

to

‘I’C(liI~Z):!

11111 ;LIld ()OCJO at

tc*llIiritc!

ITCIXlrC ;iIltl

il

solid

clitl~imnc

:Ic1tcl. Chi~ll. AC/n.

38

(lOb7)

et2 l--.)3‘+

K.

432 the presence tlw clithizonc (IV) reaction

MARIiESKI3,

IS. 13. SAS1,EI.I.

of chloride oxidation (SW later)

makes interpretation of the composition difficult. Presumably procluc:t postulated to bc formecl in the dithizonc-tclluriumis present in the mixture, but ammonia decomposition sccmccl to ShOW an kf2Dz/'l'C2 ntiCJ of 2. f-fO\W!VCr, OthCr ~~rCp,?riltionS (hdding One formed acid solution) ~a\‘c hifiller ratios. in pcrdlloric It may IX nicntioiiccl in this connection tllat wiicn finely powdered elcmcntal tellurium is sllakcn \vitil a chloroform or c;lrbon tctracllloridc solution of ditlhonc (in tlw prcscnce of air), tlic solution hcomcs greenish Iwwyn after some days. Coinof clitliizonc to tellurium clitliizomitc is appilrCIlt1y not possihlc. plctc conversion Solid ‘I‘cO:! ;ilso rcwts witli ditliixcmc in cilrl>Orl tctracllloriclc to gjvc tellurium dithizrm;ltc, but more slchvl>* tlian tclluriurn. Attempts to ScplriltC! c~lroni;Ito~r~i~Jllic;illy tlw components of iln :Llcollolic solutioil of tlic solid illJC)VC! on a mixture of Al~O:~ :lncl lil-ISO.;. wcrc uIlSUcccs!!fUl. attcnilds to sclJar;itc tlic coinl)oncnts of c;lrl)oii tdracl~hritlc cstracts Likc\viw, wcrc’ not fruitful.

‘l’llc cXtrilctC!tl tellurium spwics ~xtr;lctiOll of one or tlic otlicr of tllcsc telluri~iiil-tlitliizonc rcnction riltio illltl [‘l’c’& on tlw C.XtIYIctioIl cocfficiciit. l
cotnbining

tllc

to consider

IIliLy

tlIcI1

IX

‘l’cO(<~H)++4 ‘I’llc 1X! Ii:is

f-Jn_l~~/‘I‘c~is 4 :~ntl

wllctlwr tllc cxtrilctc
W

ratio

tlw is not ‘I’c(I-1Ih). s or ‘TcO( I-I lh)~. Certainly as tlic main spccics is not in accord witll tllc tltc effect of tllc V~lriilblcs LI-IcDZ],,, [I-I’+] ant1

p: ‘l’c!(Hl>x):!+

cffcct of tllc Vilri:1lDlCS IncI1tioIiccl (I-II)X)z, llot D;z (tllc c~rhdiilZ0Ilc). not IMXI~ prcpwccl. l’rcsurnnbly 1’11-9 ZT N-C .z s-i\i

IHIh):!+H~~+2

0

0

slwc*ics is not ‘I’c(HD~)~.‘l’llc

tllilt

‘1’llC

IIC)StUliltcd

it is the

I-Id)

W

0

rccluircs

cstrnction

tllc

cJSithtiOI1 cOlllpC~LIll
product (FiDZ)2

of tlitliimne

apparently

clisiilfidc

).I-I’ll

I s I s I I’ll-s-E

x-c

= N-5~-I-I’II

l’llc cviclencc for tlic prcscncc of more tllalr one ill>SOrbiIlg species in the Cilrhll tctrachloritlc cstract is rcnsonal>ly goocl. \Vc tilkc tllc oxichtion product (or products if neccl IX) to represent a11 or most of the aclclitional nl>sorl,ing spccics. All t hc (principal) reaction products Ilavc similar nl~sorbancc curves, as \vc liavc swls. The presumed peak in the vicinity of 435 mixtures of ‘I’~(HDz)z and (HD;r,)c SIKW an absorption nm (Figs. 7,1-d), whcrcas Tc(HDa):! sllows a peak at 450 nm (Fig. x2), at the same

‘I‘C(Iv)

01;

CtEhCTIOS

433

\VITH DtTHI%OSE

or wry nearly tlic smx wivelcngtl~ as tlw secondary peak of clithimne. e at CR. 435 nrn for (mkj2 is rouglily 40,000 (a little less), or about t\vicc that of clitliizom: at tllc same wavelcngtli. It is of interest tllat aI~~InoI~i~l-~Vi~Sll~d carbon tetracliloriclc from mixtures of HzDc, ‘I’c(HIh):! and (H1h)!~ sl~owecl H~I>z/‘I‘e ratios ranging I .c)s to 4.7, wllicll is taken to indicate tllat (HD;z)- Imrtitions into hsic ~(~uwJuS solutions. but less casilv than HcDz, so tllat most of \\‘ilsllcd cstrxts containccl the (I-IIl)z):! in adtliticm to ‘l’e(HD~):! but littlc HzDz. A ratio of 4 would rcprcscnt W~UiIW~lilr Inisturc of tlwrcaction products. frcct from tlitliizonc. 21s ~\lrCi~d\‘I~~cntionctI. ;i good scIxlr:ttic,n of tllc cornponcnts cannot 1x2 old;iinctl bJ* ;mi1imii;~ \VilSlliIlg. I’rcsulllili>ly (lJI>z)z forms HIh:!-- in lwsic solutions wit11 ilI1 ahorpt ion lW;lk IlCilr tllilt Of HIJZ-. (470 11111)I>Ut \vitlI i\ IilrKCr c’. SicJtll;lt it will IN! CoUIltctl i\S ill1 appro.silniltcl~ C!(llli\‘illcIlt ilIllOIl?lt cJf ~1itlliZ~JIliltc ion. ‘I’lw cstradicm ~OIlSt;lI~t of tellurium Iron1 tlIc forcgoinC: WilCtiOl~ cclUiltiOn iS I\‘,.,,

=

[-I‘(: (H 1.h)~ .,,I (HIh)z?],iH’i

_--

---7.--

._.--._-

[ I Co(o~.i).‘.;EH:!l)z:,,.’

‘I’llc oStrilctiOI1

c~c)c*ffic*icwt (Jf tclluriurn

tlIcI1 is

hccordinC: to tllis cslwcssion I:’ ?illolll(l \‘ilry :ls ! I-I~l.)X~,,2, i l-I+; -4 illlcl i,TCO(OtI) +‘j-. b if tllc pW~l~JI1liIlilIlt spwics in tlIc ;I(luw~us l)li;isc is ‘I’cO(OH)+. i.c.. if ‘I’cO(OH)q is ncgligiih. Over tllc lxirt of tlw rilIlK:c inVcSti~iltc(l (tlitlIi;r.oIw in c!XCCSSover tellurium). tllis CSp’CSSiCJIl for IT l1olclS rCilSOIlill>l~ \vcll. ITrc)Ill tllc 4 curves in FiK. H, tllc? foIlowing VZI~UCS of log l<,.x, ilrc C;IICUliItCd: f).?(O, 10.74, 10.42 ;111d 10.X<), iIVCritKc of 10.~3. I=roIn I:iK. 11, 10~ lCcxt = IO._+. I\‘ck, ) ITl;l?, IX? tnkC!ll iLS IOG.*5, or ill>OIlt I .5 ’ IO’, ilntl this VillUC can tlwn 1x1 usctl in tllc cslwcssion for !~l’c(I-II>z)~]o/[‘l’cO(<>I-I)~~j to 0lJtiliIl tllc distribution of telluriutn Iwtwcen tlIc: 2 lJllilSCS. l;or e.S;lllllh!, it Illily IX (cn. I.3 p.p.111. ‘I‘C) ill I 1%f (‘illCUl~ltColl arc Sllilk(!II to~ctlicr to ccluililzriun~, il}~l~r~JSiIIlilt~!l~ <]ti’I,;, of tllc tellurium will IX CStrilCtMl. A scc.ontl tlitllixonc c?str;iction will twnovc’ approxinlatcly (.V).llilsc (;lsstl~~linC: tllilt ‘I’~(HIJz)~ in tllc il(luCC>Us l’llilSC! C;\Il IX ncglcctcd). ‘I’llus it ITlily lx cspcctcd tllilt Inicro~r;~nI quantities Of tellurium Cilll IX? CStrilctCtl from ilCi
\Vitli nn cxccss

of ditliizxmc ovcretcllurium,

tlic cstraction

of ‘I’c(IV)

from I M

pcrcliloric xicl tile rclntion

into ;t cnrhn

solutions

[TC(Hl)Z):!~<, -[‘I‘(!O(OH)

=

I.5

*

follo\ving

rcliltion

Sw:flIS

[‘I-c(HDx)2],,

__-.

=

to

qpin 1X

\vitti a sufficiently

;l]~]~r~~iLCIlCtl

(0) of clitliiaonc

follows

larg:e

c’scc’ss

of

ditllizone,

tllc

:

[)_~:!1~~~;,,“[“l‘CO(OI~I)

.I()”

I.5

Solution

~f-i~I~z~,,“[,‘l’co(ol~I)~‘-~ ’ .

IO"

‘-i

\Vl~cn tllc acidit>* is \*arwd,

tctrxliloridc

’

‘.I-‘[H-‘-j

(p =

X.0).

~‘I’co(~~f-I)“-]

I.rJrs ilU

ii3oycn

(1’1111

CSCGS

dc I’cXtriLc:tion sfJllltion


tlitllimnc,

Ofl

r*rc(w~)2~c,

_!--_..

----

[‘I’cO(Ol-I)

Lorsclu’i~ii vcrs

Ia

I=

X.5’

I’xitlitc!,

cliangc

rcliltion

‘. I

tlu tc:llurc(IV) tic tlitllizclnc il

Ii1 rc’htion

c’n solution

10’11f-?:!l~xj,,“l’~l’c0(011) ;lVCt:

clans I’ilCiClC 1x2~c:llloricluc I &I,

(Ii1115 Ic tc~trxl~lortirc :

1111 1:.X&S

tic c;trlmw.

cn prCwnc*c

1.1 1

S~lffiSilll~llI~tlt

grilllcl


011

tclltl

:

--[‘l’c( 1-Ilh)‘L!c, [‘l‘co(ol-i)~‘~~

=

I .s ’ roS[~I-f:!l)%!,,“[’ fCO(OII)‘~j

“[f-P]-

’ (p-

1.0).

1:s wird tlic I’:XtriLktioIl von ‘I’cllur(IV) nlit ‘l’ct~~~ir~l~lorkoli1ciistc~ff untl cincm GIxrschuss an Ditllixon iius I M lxrclilorsiiUrcr J,iisunC: hcscllriclxm. Fiir die Vcrtcilung clcs ‘l’cllurs wcrclcn \!‘crtc in Al>lliingiKkcit van den ]ioll;l.cntr;itioncn tics ‘I’cllurs, ties Ditllizons uncl dcr I-I-Icmcn i\ngcpl>crl untl cntslmcltcnclc (~lcicllun~cn i~Uf~C!StClIt.