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532 ANALY TICA Cl1 IMICA ACTA

IS fIicJI~UC.TIC)N

‘I’hc rcactionc; of platmum, p~dlnclium and gold chlordcs with 1dicn;~nthroline in

chloricle or thiocyanutc solution huve already been studicd hctcromctrlcally~. The
various compuncls ohtxincd have been cliscusscd.
‘1 hc prcscnt report clcal~ with the actual tletcrmmations of the metals singly ancl
in matures. WC huvc already shown that the scnsltlvity of the phcnanthrolinc-noble
metal rexction is lower than that wltll other spcclf~c xnd complex mtrogcn cornpouncls.
(A study witI> pxpavcrmc will lx prcscntcd later). However, tllc sensitivity 14 often
not the dccisivc criterion of tlic importnncc of a hctcromctric reaction. Thus, pllcnnn-
throlinc presents a scrics of lietcrometric reactions ancl coml~ouncls wliich can bc
appliccl successfully for the precise, clircct cletcriniiiation of all the rnctxls present m
ml\turc+ without any previous scparutions whatsocvcr.
‘1’1~ impcdxncc of tlic propo~ctl mctliocls is that two or three noble metals in an
alloy (or in a solution of chloritlcs) can lx detcrmiilcrl from the CrltiCiLl points of
one titration curve only, ix. two noble mctnls, forming cliffcrcnt msolublc compounds
cdii both 1x2deterniinccl accurntcly from the samTIclicturomctric cu~vc.
‘I‘lir sim~ittancous d~tC!I’l~lltlilt~~Jtl of lhtinuni ant1 palluclum~ or gold nnd palladium
rCcpln-cd only 3, mg of .illoy , tlic tlctcrmination of gold ‘ulcl plntinum rccluircd at least
clolllh tllis illllOU~lt. Ckncrully the third noble metal pt-cscnt could lx dctcrminccl
from the diffcrcncc. ‘I’hc tlcterminatlon of all three metals in an alloy or in a soluble
misturc of cliloriclcs in scvcrnl ways by two scparatc hctcromctric
was possible
titrations. A titration li1StC’tlabout IO-15 min at zoo. 111illmOSt all C;lbCSstudied, tllc
sccoiicl rnd-point (11) agccrl c.\actly wit11 tlic thcorctlcnl sum of tllc amounts of
xnct;d.s tlctcrmincd. Sonic crroib occurrccl at tlic last andyt~cal intcrscctlon point (1)
(first cd-point), but tlicsc could 1.x avoiclccl by prncti~c

‘LX2 \;knic rcxgcnts ant1 working conclilioiis wcrc* t~scctits iii previous rcports2~3.

I11SbU1,l s
Table I clcscribcs a scrics of llctctomctric tltrnttons of mixtures, chiefly of two

n Mll CllrrIl Acftc, ZL (r9Go) 532-538

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HETEROMETRY OF Pt, Pd AND Au 533

metals, with phcnanthrohne. The course of a few trtratlons is also shown in Fig. I.
I3efore the different methods for the determination of the metals arc indicated, the
working principles and the results are drscussed.

ml

In the ca5c of platinum, it is posslblc to keep tlic platinum dissolved or to dctcr-

mine the platinum simultaneously with one of the two other nohlc metals prcscnt.
Probably any quantity of platinum could remain c~lssolvccl in chlorldc solution at
1~ 1-7, or in thtocyanatc solution at about 1~117. I~allacllum and gold wcrc both
precipitated clthcr in chloride or thiocyanate solutions at p,r x-7. Thcrcforc, If both
are present, they can only be dctcrmincd from two different critical point5 of the
titration curve. The platinum wa.s precipitated from acid thiocyanate solution only,
thus the insoluble platinum thiocyanatc compound coulcl al50 bc dctermincd from
an interscctlon pomt of the same curve.
In all the casts given, only those metal-phcnanthrolinc compounds which func-
t ioncd as finalcompounds (11) were of analytical value If the single metal nnalyscd
was titrated under the same working conditions.
The presence of chloride in large excess seemed to have no influence on the results.
The influence of the concentration of the thiocyanate varied. Generally (especially

Aaal. Chim. Acla, 22 (1960) 532-538

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bl. UOBTELSKY, M hl. CdIiEN

Ccncrd composlt1on u ml rcagcnts + (IO-U) ml H&

______ ._ .--._ - _ -- -._-- _ ._._ . __-__.-___ __ .____- ..___ __ .

x/Jr
VU
. _

I 3 1n1 0 00.1 AI I I~l’tCl,j -t_ 3 1nl 0 00.1 IV? lJtlCl~ 64 7% 35 3%

-C I ml Af I-INOS -j- 2 ml M NrrCl 2 3427 I 28oq 0 005

2 3 11110 001 M I-Izl’tCln -I- 4 1nl 0 001 k? i’tlCl2 57 8%’ .)2 2 ‘7”
-I- I ml Al lINOl + I ml 0 15 hf ICCNS I 1714 0 8536 0 01

3 3 ml 0 00~ M IIzl’tClu -I- ‘1 ml 0 002 &I I’tl(.lz 57 8% 42 2 ‘%’

-1 I ml N IINO., -{- I ml o 25 Ad KCN“ I 1714 0 8536 0 01

4 3 ml 0 002 M IIz13.Clo -I- 4 ml 0 002 121 I’tlClz 57 8% 42 2%’

-1 I ml 3 hf lINO j -k 2 ml 0 2.5 IV/ ICGVS I 171.1 0 8.536 0 01

5 3 1111 0 001 n4 1 l,lW I,, -I- ) 1111 0 002 Iv2 Z’dClz 57 H’i: 42 2 %
-t I ml nr I-IN<& t 1 ml nd ICC’KS 1 1714 0 8536 0 01

0 3 1111 0 00.) ICI I Isl’t(:l,, -I- ) ml 0 005 111 I IAu<,l,, 37 3% Gr 7’zb

-+ I 1111 nr I I NO, 2 3427 3 9440 0 005

7 37 3% 62 7%
2 3417 3 0440 0 005
H 3 ml o 00.1 AQ II~l’tClo -I- 4 11~1o 005 M IIAuClt 37 3% 62 7%
-I- I 1111Af I-INO3 -t_ I ml o 25 AI ItCNS 2 3427 3 9440 0 01

9 3 7x110 004 M 11~l’tLl,~ + 5 ml 0 005 M I-lAuC1.1 32 2%’ 67 8%’

-I- I ml hl lINOn -I- I ml o 25 AJ I<<.NS 2 3427 4 0300 0 01
I0 3 11110 004 Af 1 I~lJLCI,, -1_ 4 in1 0 005 IV 1 IAuC1 I 37 3% 6.? 7%
I- I ml iv/ IINOJ -k c 11110 5 Af ICCNS 2 3427 3 9440 0 01

I I ‘, 1111 0 00.) M I-Izl’tC’l,, -1 2 1111 0 00s IV1 I IAUC 14 61 3% 3cJ 7%

-I- I ~111AT I-INOn -1 2 ml o 5 Ad I<C.NS 3 1236 1 9720 0.01
12 3 ml 0 0o.l M lI2l’tC I,, -I- 4 ml 0 005 IV 1LAuC 11 37 3% 62 7%
-I- I 1nl M Na-accta.tc! -I- I ml 0 25 M ICCNS 2 3427 3 0440 0 01

‘3 3 11110 00.l nf IIdw I,, -I- 4 nil 0 005 iv IIAuC.l, 37 3% 62 7%

-I- I 1111 kl N.wwctatc -I- 1 1nl o 25 ICI ICCNS 2 3427 3 0440 0 01

’4 3 ~II 0 oo4 ILI l-IaI~tu, -I- 4 11110 005 nr i-ihc1, 37 3% 6.! 7%

-1 I ml M N;r-acctntc + I 5 ml o 5 M KC’NS 2 3427 3 9440 0 01

I.5 3 nil 0 004 fV1 I-lal’tC’l,, -I- 4 ml 0 005 M 1-lA11Lld 37 3% 62 7%

-I- I 1111 AI Na-awt.rtc* + I J=’ml fig IC<.‘N~ 2 3427 3 9440 0 01
I f’ 3 nil 0 002 hf l%lCl~ -I- .I ml 0 0025 M Ilf\~iCl,~ 2.1 5% 75 5%
-I- I ml M Na-acctirtc -t_ 2 ml o 25 M KCNS 0 Gqo2 1-9720 0 01

‘7 3 ml 0.00‘) IIf/ I-Ior’tc:l,, -I- .? 7111 0 00.) n1 I’d< I:! 12% 55 2%

-I- ‘1 ml 0 005 M I-lt\11Cl4 $- I ml M IlNO., 0 8.536 3 9440 0 01
18 3 ml 0 00,{ n’I l’tlc 12 -}- .I 1111 0 OOZS ~!‘f I-IAuc14 3’) 3% 60.7%
$ I ml fW Nn-ncctntc -/- I ml o 5 IV ICCNS I .2804 1 9720 0 01

19 a) ml o 004 111 I’clClz -t_ 3 1111o 0025 M l.IAuC14 53 5% 46 5%

-1 I ml IV N+acct:rLc -t_ I nil o 5 A1 KCNS I.7072 I.4790 0 01
10 3 ml 0 005 nr I Isl’tClu -f- 3 ml 0 004 fir PtlCla 40 8’g 18 o”/a 4 1 2%
-I- 3 11110 005 ill Ilr\ucld -t_ t ml hf IlNO:, L 9&.) I 2Y04 2 9580 0 01
21 3 nil 0 005 Al I l~I’tC:lo -I- 3 n11 0 004 iW I’tlCl~
-I- 3 1111o 0015 M l-l,\uCl , -I- I 1111M Nn-act 51 4% 22 5% 26 1 “/o
-I- 1 ml 0 5 IV ICC INS d 9284 I 2804 1 4790 0 01
----_- .--- .-- -______-____-_ _____ - - _.___
____-___-_-__---
= Corning yellow filtcr (348,1), c = contact point, Ii = tiori~ontnl mnx1mum tlcns1ty Irnc, 1 = mtcrscl

A~uaZ Chrtn. Ada, 22 (1960) 532-538

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IICTEIIOMETRY OF Pt. Pd AND AU 535

TABLE I
r ml AZ b plicnanltlrotmc (= P) r‘ = 2c.p
--- _- ---- _---_ --_- --_ __-- --- - -- - -~-- -_-_- __--------__---
1 orrod I- *Id/tanI TJlra-
_ - --- __-- _ _ __ --- --- I to,,
lntld pp1 r”fcrmcdlnlrt- - -
OptIcal _, tInI.
rom@wtd ml OJ I’
at CO’?lpOtld.~
dcnstty “’
II “$VW5& ml C’ 06tacncd rrror
I”
I’ Jorn’rd orcrd tdur P’ll”
-_ ----_ -- _- __
-_ -- __- __-_- - __ --___-__-- - ___ _ - _ ------ I_ ----_-I ------

f’dst’at 1 3 60 h I’ti21’4~ o 66 0.0 I2

1360 h I’cll’r~~ i- l’tl’,ll 0 74 0 0 ‘5

l’dI’,ll I 3 00 I1 l’dl’,JJ -+- 1’1I’nlJ 0 50 00 I.?

I’tll’,ll (J) I 3 Go h l’<ll’,~~ -+- 1’11’2lJ 0 52 00 5‘

1’dl’eJ -’ I’ttt’nll I 3 60 II l’clIJ3J~ + I’tl’r~~ 0 36 00 ’ 4

J\ll,t’21 1 J 00 II J\llk’&1 0 4’) 0 0 ‘3

4112l’l -* Jh171’21 1 ,t OC) I1 \lll’&l 0 .+I 0 0 ’4

I’tst’nl -* t’t.1’2~~ 1 3 40 la t'tt',ll -+- .\1121'11 0 7s 0 0 12

- I’tl’l -- I’t*l’,l I 3 7” I1 l'tl'ul~ -I- \1121'~~ 0 76 00 II

- I’CPn~~
lY11’31 I 3 40 11 I’tt’all + .\urT’JJ 0 70 00 12

1’WJ -- IJt2I’ll I 3 70 I1 I’tt’n~~ -t ~\Ll,l’~~ 0 82 0 0 Is?

1 tooIl .\ul'244 0 40 0 0 I2

I .t 00 II \uI’24l x0 59 00 11

hu,l’a& --* .\114l’al 14ooh J\t11'21& 0 72 0 0 12

1 ,t 00 h r\ur'n~~ 0 32 0 0 *7

All2l’,l --, AuL’ell 1290 II r\\ll’2l~ + l'tlal',~~ 0 57 00 14

J\U#lt -’ J\llt’11 13 2011 AllI’ll -+- I'tl21',~& 0 74 00 ‘3

I 3 Ho I1 \Ut’21& +- t’d21’311 0 93 00 ‘3

Aunt'4 - hlll’2ll I 3w 11 J\llr’244 j- t’tt21’211 0 QI 00 ‘4

J\llt’&$ 1 3 30 tr AllI’ll -#- l'dnPe~& 0 78 00 ‘3

11; * so AllPl’2~ - AuI’all 133oh AuPnl& + PdeI'a3~ 0.8.) 00 ‘3

--- ---- --
In point.

Anal. Chim. Ada. 22 (1960) 532-538

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536 M. BOBTELSKY, M. MI. COHEN

at about PII I) thcrc was an optimum concentration of thiocyanate in each case. An

cxces\ of thlocyanatc dccrcnscd the maximum optical dcnslty values, although the
composition of the final compound usually remained unchanged. Large amounts of
acid also hacl an atlversc effect on the dctcrmination. Thus the best results for pla&-
num and palladium (Expts. z-5, Table I) were obtained with a minimum quantity of
thiocyanute, although lxzlow ;Lcertain lcvcl of thiocyanatc the results become uncertain.
In the cletcrmination of platmum andgold (Expts. 8-x1) the first end-point (I’tPz) was
rcliablc only if a minimumamount of thiocyanate wnsused. In the prcscncc of an excess
of thiocyanate a cliffercnt platmum compound was found (Pt&). In all these cases the
maximum optical density value rcmainecl the same (Expts. H-10) In acetate 5olu-
ttons (Expts. xz- IS), the platinum always remained dissolved. The final gold com-
pountl WELTalways of the same composition (Aul-‘~), but the mtcrmcdlatcs traced
were thffercnt if more thiocyanatc was used. The optimum quantity of thiocyanatc
sccmctl to bc somewhat larger than usual m thcsc cxperimcnts (Expt. 14). The ratlo
of the metal5 m the test solution could also influence the result ; WC did not cxamme
this further.
'Pf\I3I,lS
II
--_ ^- -__ -. -._._ - _ -. _
hrledr hrrlols A ppmx ,,,g tnrlnl
Pfl fC;-
prc S‘III rlclc’?nlrtInl us UW&VCd
----_ - __-_- _____ ___ _.. _.._ --_- . ----- --- ---- - _- . ___-_

I Cl- I%, I’d l’d21’3 35

I LNS- Iv., I’d I’cll+j (I). I’tl’l (I)
I Cl- 1’1, l\ll All I’ ;j
I ('NS- IV, r\u I’tl’3 (I). Au.dlJ(2) 5-b
7 ( NS- IT, All hlll’a 0
7 ( NS- I’d, All AlII’J (I), I’&!l’~I (I) 25
I c l- I%, I’d, Au i\lll’ (I), I’(I:I’J (I) G-7
-_- -_._---___~---__-_- - - . _ __ ._ _ _. _

l’ablc 11 rummnrizcs the ftnnl compounds obtained. ‘I‘hc numbers in brackets show
the or&r of formation of the compounds, this dcpendcd on the composition of the
test solution. Thus in mixtures of platinum and palladium in thiocyanatc solution at
about plr I, the pallacllum was precipitated first; in mixtures of platmum and gold
(under the same conditions), the platinum came first, whllc in mixtures of gold and
palladium in all casts the gold precipitated first. l’or the dctcrmmation of a single
metal, approsimotcly x mg of palladium, x -2.5 mg of platinum and 2-4 mg of gold
wcrc ncccssnry.

MI31 IIODS
GctLcml ror1n?4s
In all the followmg methods, the error at the first masimum optical density point
was always approsimately qua1 to zero. The last intcrmcdiatc intersection point (1)
was always obtained from the intcrscction of the two adjacent lines (branches) of the
titration curve.

About 3-4 mg of platinum as chloroplatinic acid in IO ml aclucous solution, con-

taming I ml of M HN03 and 1-2 ml of 0.5 111 KCNS, arc titrated with aqueous

Anal. Chm. Acln, 22 (rgG0) 532-538

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IIETEROMETR\'.OF 1%. Pd AND AU

537

0.01 M phenanthroline. The end-point appears at the first maximum optical density
point, comcidmg with the quantitatl’ve formation of PtrPp.

2. Determnntion of ~lnlinwt and ~nlladaunt

About z mg of the mctnls, as chlorrdcs, In IO ml of solutron containing I ml of M
HN03 and I ml of 0.25 IV KCNS arc titrated with aqueous 0.01 111 phenanthrolinc.
Two critrcal points arc obtained. The frrst pomt, which IS the last Intermediate
intersection point, appcnrs when PdrPa is quantitatively precipitated. The second
point coincides wrth the first maximum optical dcnslty point, giving csactly the
sum of PclrP3 and PtrPz.

About I mg of palladium a.5 chloride m 10 ml of aqueous solution containing 1 ml

of Jr HNOa and I ml of IV NaCl, is trtratcd with aqueous 0.005 ;1Z phcnantl~rolmc.
The first optical maximum density point comcidcs exactly with the quantitative
formation of PclzPa. The trtration can also be carried out at cu. PI-I7, using I ml of &I
Na-acetate instead of the acid. The solution may then contain I ml of Jr KCNS
mstcad of the N&l.

*rhcprocedure 15 the same as in 3, with chloride solutions.

About 4 rng of gold, as gold chloride, in IO ml of aqucour solution, containing I ml

M of Na-acctntc and 2-3 ml of 0.25 111KCNS, arc titrated with aqueous 0.01 111
phenanthrolinc. The first optical maximum density point comcidcs exactly with the
quantitntivc prccrpitation of AulP2.
‘The same titration crln bc carried out in iIc?d solution, by rcplacmg the Na-
acctatc and the KCNS by I ml 111HNOa. The titrant is then 0.005 ;\I phcnanthro-
line The end-point appears at the quantitative formation of AurPl. The former
mcthocl is prcfcrablc.

About 3 mg of the metals , as chloriclcs, in 10 ml of aqueous solution, containing

I ml of III Na-acetate and 2 ml of 0.25 111 KCNS, are titrated with aqueous 0.01 i\f
phcnnnthrolinc. Two critical points arc obtained, the first point (i.e. the last intcr-
mccliatc point) comclclcs with the qunntitatlvc formatron of AUIPZ. The second point
(t.c. the first maximum optical density point) coincides exactly with the quantitative
formatron of the sum of AulPz and I’d&.

7. l>ctevntinatio9t of /datinitnt and gold

About 5 mg of the metals, as chlorrcles, in IO ml of aqueous solution, containmg
I ml of ~11HNOa and I ml of 0.25 M KCNS, are titrated with aqueous 0.01 Ad
phenanthroline. Two critical pomts arc obtained. The first point (the lnst inter-
mediate point) coincrdcs with the quantitative formation of PtJ’2. The second point
(the first maximum optical density point) coincides exactly with the quantitative
formation of the sum of Pt& and AuePr.

Anal Chant. A&z, 22 (rgGo) 532-538

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538 M. BOBTBLSKY, M. M. COHEN

8. Determination of +henantlwoline
About 4 mg of phcnanthroline in IO ml aqueous solution, containing I ml of ‘WI
Na-acetate are titrated with a 0.004 M solution of palladmm chloride. The end-
point, at the frrst maximum optical density point, coincides with the quantitative
formatlon of Pd2Y3.
The test solution may contain some sodium chloride. The analysis can also be
carried out at about PH I in nitric acid solution, but the former method is prcferablc.

SUMMARY
l%tlnum(lV), pnllaclium(lI) and gold(III), 8s chloriclcs, wer0 clctcrmmcd dlrcctly in tlliucy-
,Lnatc or clllortclc solutions by hctcromctrlc tltr,rtlon with phcn~nthrollnc at phi values of I - 7
L’WO Or CVCn tllrcc nl&lls COUld be dCtcrmlnCd ~IrCClSdy lronl the CrltlLd pJlnt5 Of One Or two
lictcromctric tltratlon curve3 Scvcrnl mctliods arc prcscntecl

14usicurs mdtlloclcs sent proposhcs pour Ic dosage du platmc, du palladium ct dc I’or, cn prdscncc
10suns clcs autrcs On procZxlc par titrafp h8tBrombtrrcluc en utlllsnnt la plidnantl~rolinc commc
rdactif.
%~JSAIMMENFASSUNG
I)urcli hctcromc*trischc ‘ritration mit I%cnantl~rolin Iconncn Platin, IJalladiunl uncl Gold
nc~l~cncmantlcr bcstimnit wcrclcn

Aural Chrm. Actn, 22 (1960) 532-538

THE ACCURATE DETERMINATION OF COBALT

A. G FOSTER AND W J WII,I,IAMS*

moyccl Ilollotuny Colic@, W~rrvcvsriyof Loudou, Loudo~t (Grenl Urllaan)

(Rccelvcd November gth, 1959)

INTRODUCTION
Pvintnry standards
The analytlcal chemistry of cobalt has been reviewed recentlyl. A literature survey
reveals the use of a wide range of substances as primary standards (Table I) some of
which have been critically discussed by YARDLEY~.

CoSO4. The important question here is whether ignition of the hydrated sulphate to

* Prcscnt adclrcss Collqp of Tcchnologp, Bristol

AIwZ. Chrn, AC/~, ~2 (1960) 538-546