VOL. 14 (1956) ANALYTIC.4 CHIMICA ACTA 4(>5

DIETHYLENETETRA-AMMONIUM SULPHATOCERATE AS VOLUMETRIC REAGENT

II. IODINE MONOCHLORIDE METHOD. 1NDlREC-I’ DETERMINATIONS*

BALWANT SINGH AND SURJIT SING13

Panlab Univcrsify College. I-iosliiarpiir (India)

In xcid medium diethylcnctctrn-ammonium sulphatoccmte, [Cc(NH,-CH,-CH2- NH,),J(S0,),.211-I,SO,.?H,O, reacts with potassium iodide:

2 cc+~ + I- -= 2 cc+3+ I’

In prcscncc of hydrochloric acid, potassium iodide reacts with potassium iodate, potassium metnperiodate. potassium dichromate, potassium lx-ornate, ccric sulphatc, hydrogen peroxide, lead diosidc ancl chlornmine-13 according to the following equations:

IO,- + 2 l- + 0 l-I+ = 3 I+ -t_ 3 H,O 104- + -3 I- + s 1-r+ = 4 I+ +_r H,O Cr,0,-2 -j- 3 I - + rd 1-i + = 3 I + -j- 2 Cr+3 + 7 l-I,0 BrO,- + 3 I- -j- 0 I-I+ = 3 I+ + I!r- + 3 H,O 3 cc+4 + I- = 1+ + 2 cc+3

0,-z + 1-j-q 1-i+ = I++2 H,O PbO, + I- -t_ 4 H + C,FI,SO,N(Na)CI + I- + 2=N+

I+ + m+2+2 I-i,0

= I+ + CeHbS02NH, + NaCl

The reactions have been utilized for the quantitative dctcrrnination of the sub- stances.

EXPEIZIBIEKTAL

A known amount of each substance was transferred to a conical flask. and 5 ml of chloroform, a known CXCCSY of potassium iodide solution and enough hydrochloric acid to keep its normality tetwecn 4N to GN were added. The cxccss of potassium iodide was titrated with dlethylcnc- tetra-ammonium sulphatoccrate (DTS) solution. The rcagcnt was added from a burette until the solution which was colourcd with iodine bccamc pale yellow and the chloroform layer acquired a purple colour. The comcal flask was stoppcrcd and vigorously shaken during the titration. Addition of small volumes of the sulphntoccratc solution was continued, shaking vigorously after each addition, until the chloroform layer was faintly violet. The sulphatoccratc solution was then adclptl dropwise, with shaking after the addition of each drop, till the chloroform layer bccamc pale yellow. The end-point was very sharp.

Several titrations were pcrformcd in each case. From the volume of diethylcnctctra-ammonium sulphatocerate (DTS) used, corresponding to the end-point in each titration, the amount of cad1 substance was calculated. The results arc recorded in Tables X-VIII. From thcsc results it is con-

* PART I was published in Axal. C/km. Acta, I 1 (19,561 rag.

406 I3. SINGII, S. SINGH VOL. 14 (rcJ56)

eluded that diethylcnctctra-ammonium sulphatoccrato (DTS) can bc usccl as a volumetric reagent to detcrminc indirectly potassium ioclatc, potasdum mctaperiodatc, potassium dichromate, potassium bromatc, ccric sulphate. hydrogen peroxide, lead dioxide and chloraminc-R by the iodine monochloriclc method.

All chemicals, cxccpt cwc sulphatc and chloraminc-13 , used In this investigation were of guaranteed purity. Ccric sulphatc was standardizccl with ferrous athylencdiaminc sulphatc. Chloramine-B was freshly prepared and standardized by an iodometric method.

TABLE I

POTASSIUM IODATH _--.-_-_L_“____ - ._._.~-.._-~----“.Ir--_-._--___ -.__. -- __..___ __ .___ _ . _ . ..- -_ - -- _ - .- - __- .---

KIO, fukcn o.oaN ICI added cr.oaN UT5 used lor o.ooN h’l ctsrd “v KlO, h-f 0, /omd CXCCIS Ki

c: ml ml ml iz - __.- - __..-_.-_- ..* -___ . _. _ _ __._-- -_. .__._ .-_. _._ -.-_._. __ _____ ___. . ___ . . ____-_ -__-____.-___ __._ _._ _ -

o.oogz 30.00 21.40 8.60 o.oL23 30.00 18.50 I I .50 o.or53 30.00 LS.70 14.30 o.or89 30.00 12.30 17.70 o.ozrg 30.00 9.w 20.10

0.0092 0.0~23 o.ors3 o.orng 0.02 t fj

.______-_ --- - - -._- . _.” _ .- _. _ _____-_ __._ _

‘I’AULE I1

rJo*rAssiu,v swrAw<NfoDA*r& .-w--e- . . .._... *_ ._--- __ _-___ ----.-.- .--- _ _-_--_- -_-- _f - --.-_ ---.“___ .

KZO, tukm o.ozN KI mIded o.osN ZXS rtscd for o.oaN Kf CXCCJJ ii1 trstd by h’l0,

g *Ill I,11 ??tl . - _. _ _.“_ - .__._ I___L-_.-._. . . . - ._ _ _ - _. .___ - . . . _ __ _. _ _ .__-_

0.0069 30.00 2r .oo 9.00 o.oog2 30.00 18.00 12.00

0.0x 12 30.00 ‘4*50 15.50 0.0 I# 30.00 12.00 18.00 0.0 163 4 30.00 8.80 21.20

. . h’ro.

/Qwlf lz

-_ _ _._. --

0.0069 o.oogz 0.01 rg 0.0138 o.orG3

-. -..__e._ .-._ _- . . -. . -.. -..-.-......_ _._. _- ._.._. _.._ __.. -_ ..__..._ ___._ -_ . . ._ . . .

TRBI..E I I1

I’OTASSIUM DICHIIOMATB _-__-_ .-_I-_- _.” -__ -*_^_ ^ .-. _ __ - --_.._---L_L-__-_-._._-.. __ _.__-. _ _ _ --_ K,CT*V, I&. tf o.wN Ki ml&d 0.03N Df’s IMCd fut am2N KI

cIccss Kf g IIll otl

rtscd by,,,$,Cr,U,

-__A_._-__--- -_-_-._- . .

0.0083 30.00 2L so 8.50 o.oro8 30.00 ig.00 i 1.00 0.0140 30.00 15.70 ‘4.30 0.0169 30.00 12.80 I 7.20 0.0210 30.00 8.60 ZL.40

_I _ , . ..___ . . ._ .

TABJX IV

._ .__ __.-. _ ._ I . _ __ K&r&,

/OWfd

G _ _--- __ _.__..

0.0083 0.0x08 0.0140 0.0169 O.OZLO

rwrhssxunt DROIHATB .- h_l,-G, . _ . . I _ _ _ . . . .._ .__. -_- __. __. __ _- -_. . ._ .__ _.. ._ _* _. __.____ __. .

o.ozN KI ml&J o.o~N Dl’S used /or o.oi~N KI cxccs5 f\‘I

fi ttrl mt rtrcd t$i UT&

_.._ __.__. I -

KUr0, fouud

tc - .--- .____ -- ----- . ..-.^.-“~-._-_ _-_ _ . - _ ._“_____. I_... . -. .

0.0056 30.00 20.00 10.00 0.0056 0.0072 30.00 x7.00 X3.00 0.0072 0 VO9L 30.00 13.60 16.40 o.oogr 0 u-14 30.00 9.55 20~45 0.01 r4 0-J 13 30.00 7.05 22.95 0.0125

VOL. 14 (rg56) DIETKYLENETET~-AMMIONIUM SULPHATOCERr\TE, I I 407

TXT3LE V

CORlC SULPIIATE ___ -_ . _ .___ _ _ . . . _ _ . --._ -._.. _-. _

O.OlN Iir ded o.o2N UTS trsed /or

. ___ ___ . . . - _ - _

Cc(SO.), ttrkm

6

‘CC~SOJ, - /Otdlld

o.oGr8 0.0811 0.0997 0.1196 o.r4tp

_ _ . __

WI _ . _ .

30.00 30.00 30.00 30.00 30.00

_ _- ._ . _ _ -.

ctccss h-l ml

. __ _

‘20.70 9.30 17.80 12.20 15.00 15.00 12.00 18.00

7.90 22.10

.I_ . . .._ . _ _ . _ I _ ._ -

17.00 I 3.00 o.oo+t 14.50 *.5*50 0.0053 II.YO f 8.20 o.ooGz 8.65 ar.35 0 0073 3.95 d3.0g 0.0089

.x .” -_. .“_

0.0618 0.081 I O.OQQ7 0.1 IQG

o-1475

_ _ _“..__ _ _

-_ II& tukea

8 . . . __2.

0.0044 0.0053 o.ooGz 0.0073 0.0089

-moorv Kl addrd

1111 .I -

30.00 30.00 30.00 30.00 30.00

1’60, tnktn

$ . .

0.0239 0.031 I 0.0383 o-454 0.0502

tnt ._1.

30.00 30.00 30.00 30.00 30.00

20.00

17.00 I &$.oo t I.00 9.00

0.0239 0.03 1 I 0.0383 0.0454 0.0502

7.00 0.0~87

XO.Q.5 0.02Q3

14.35 0.0384

17.25 0.04Gx 21.90 0.0586

C,IS,SO,N(NU)CI JN,(J tukm

R _ “__

0.0187 0.0294 0.03s5 0.0463 0.0586

oo2N lil addctf

ml - .

30.00 30.00 30.00 30.00 30.00

in prcsencc of 4N to 6N hydrochloric acid, dlcthylcnetetra-ammonium sulphatoccrate was used as 5 volumetric rcngent to dctcrminc indirectly potassium iodatc, potassium metapcriodatc, potassium &chromate, potassium bromate, ceric sulphate, hydrogen peroxide, lend dioxide and chloraminc-B by the iodine monochioridc method. An excess of potassium iodide added to each

408 n. SINGII, s. SISGII VOL. 14 (rc)fjG)

of the su1st:uncc.s III lt~c acid mcclium was titratctl IJack with ;L standard solution of clicthylcne- tctra-;inimonlum hlltt~tlil~~~C~‘riltC. ~tltOr~JfOrn1 was uscct ;LS an indicator. Lt was cot~nrrecl viotct owing to the Ill)ctaticln uf ~otl~r~c during the titration anti bccanic very pnlc yctlow at ttic cntl- pojnt L~crru~c of the formatmn or ioclinc monochtorltlc.

J-c sulfate tic tli(~ttiyllncclininino)-c~riurll (IV), cn prdscncc tt’acitlc ct~lortlyclr~quc r( b GN a bt6 utitisd ccimmc I’GilCtlf purr Ic closagc volutn~trictuc* inctlrcct clc I’icdatc, tlu ni6tapcriotlatc, ilu cl~clirumatc ct tlu l)rc>inirtcb tic ticdassium, cl11 hll t fate cbriquc, du pcrox?;clc tl’tiydrog:tnc, tlu tllc).xytlc dc pIunit) ct tic la chlornminc* 13, par lir iiibttic~tlc iLlI monochlorurc tl’iorlc. I,‘cxcL=s tl’iotlurc ttc p0tilSSillnl, rrjclutb 2i ctincunc ttc ccb slll~stauccs, cn miticu acitlc, cst tit& par iiiic solution ~tillOl1 tic hll tfiLtC ttc tll(~ttlylbrlctliilnlino)-c~riill(lV). 1-c ch~~JrOfCmllC! cst iitllisd coinmc inclicil- t.c*iir; iI \e cotorc cn violet par I’lcdc litdrc~ ~)cn&int Ic litratfc et clcvrcnt jautic tri*s pAtc* illi point fiid pal ftrrrnatloii de n~oncd~torurc d’ic~lc.

JhS CCr( l\‘)tlllil~t~~lclltli~ltn~ll)Slllfi~t, tvurclc III Gcg:cn\v;rrt vou 4-bhr Saletlurc nls RCZL- gcllZ tlir tlic inctircktc voluiiictrischc lirst~mniuii~ voti Jrdat, ;\lctilpcrjoclnt., 13lcllromiLt. lG~liumtiroinilt, CCr9Utfilt, Was~crxtolft,croxy(l, 13lcitlic,xytl untl Chloranlin J3, nach tlcr Joct- rnont)clitoricl-i\lctllc,tlc vcrwcnttct. I>cr OI,crsctittss an I~iitiiirnjrditl clcr zu jctlcr tlicscr SulJst;~n~cli zu~cp2l~cn \vurctc, wi rtl in saurcm hliticu niit cincr ‘I’itcrlOsunK van Ccr(LV)tli(~rttiylcti- tliomin)sulfrrl Ctricrt. Dns Chtorofurm wirtl ill\ tnttikator vc~wcntlct. Es farbt .sictb viol&t tlurch iti& w!ihrclict dcr ‘t’ltrirtion III l:rclt~clt g:cscCzt.c Jod lint\ wird ilrn ICndpunkt durctl tllc: 13ildung v~ii Jodmonochlord t>t~~SS~~ll>.

I<ccc~vctl J IIIIC: r3rtl. I 955