VOL.

11
(2016) ANALYTICA CHIMICA ACTA

THE MECHANISM OF THE PLATrNUM INDICATOR ELECTRODE

IN ARGENTOMETRY
by
P. L. ALLEN AND A. HICKLING

DePartment of Inorganic and Physical Chemzstry, LiverþooZ Universitv (England)

INTRODUCTION

In thc potentiometric titration of halides with silver nitrate, a silver indicator

electrode is normally used and thc theory underlying thc proccss is quitc
straightforward. It was shown by MÜLLERI , howcvcr, that platinum, gold, and
a number of other incrt electrodes also undcrwcnt a changc of potcntial at thc
encl-point in such titrations, and a platinum electrode has been used in
argentomctry2 and in a very precise mcthod3 for the determination of the salinity
of sea watcr where it appears to be superior to the silver electrode. It is by no
means obvious why an inert electrodc such as •platinum should respond to
changes in the concentration of silver ions, and the object of the present '.vork
was to ascertain thc naturc and mechanism of the potential which is sct up.
EXPERIMENTAL

Potcntiometric titration curves werc obtained at room tcmpcraturc (IS O C) in

thc conventional way using a potentiometer-voltmeter circuit. Thc indicator
electrodes wcre, in general, thick wircs scaled into glass tubes so as to expose an
area of 1 sq.cm; the rcfercnce clcctrode was a mercury-mercurous sulphatc half
cell' (Hg/I-Ig2S04 in saturated K2SO,i). All potentials quoted arc cxprcssed on
the hydrogen scale.
RESULTS

References p. 474
 P. L. ALLEN, A. HICKLING 11 (2016)
Effect of pc-treatment of Platinum surface. In Fig. 1 are shown four curves for
the titration of 25 ml of 0.1N sodium chloride with 0.1 N silver nitrate using a
platinum indicator electrode which had been treated in various ways. Curvc r
was obtained with a platinum electrode which had been immersed in cold con-

468 VOL. ccntrated hydrochloric acid for 1 hour and rinsed with distilled
water before use. Curve 2 was that observed with a platinum electrode which,
after cleaning in cold concentrated hydrochloric acid, was heated to redness for
5 min and then uscd in thc titration. Curve 3 was found with a platinum clcctrode
which had cither becn immersed in 50 0/0 ammonia solution for 30 min bcforc
use, or had

50

Fig. 1. Potentiometric titration of chloride with platinum

indicator electrode.

been anodically polarized in IN sulphuric acid (100 milliamp for 15 min). Curve
4 was obtained with a platinum clectrode which had been cathodically polarized
(100 milliamp for 15 min) in either IN sulphuric acid or IN sodium hydroxide,
and this curve was identical with that using a silver indicator elcctrode. The
abovc curves were found to be quite reproducible, although other methods of
trcatmcnt of the platinum such as cleaning in warm concentrated nitric acid, or
by anodic polarization in IN sodium hydroxide gave rather erratic results.
It is noteworthy that at the end-point of the titration and when the silver nitratc
is present in cxccss, all the curves in Fig. 1 merge and coincidc with that found
References 474
VOL. 11 (2016) PLATINUM INDICATOR ELECTRODE
using a silver electrodc. It is in the early stages of the titration that the potentials
differ, and methods of treatmcnt tending to reduce the platinum surfacc give the
nearest approach to the behaviour of a silver electrode.
Establishment of equilibrium between Platinum and silver ions. On immersion
of a platinum electrode (cleaned by cathodic polarization) in solutions of silver
nitratc of different concentrations, the potential ultimately reached was
practically identical with that found for a silver elcctrode in the same solution.
An appreciable time, however, was required for the potential to become steady,
the time being longer the lower the concentration of silver ions. This is illustrated
by the poten-
p.
tial/time graphs in Fig. 2. No steady reproduciblc potential '.vas reached on
immersion of a clean platinum electrode in sodium chloride solutions, showing
that its potential is not directly responsivc to halide ions.
Detection of silver on the Platinum surface. The previous experiments strongly
suggest that a clean platinum clectrodc becomes coated with silver on dipping
into a solution of silver ions. That this is so haslbecn demonstratcd
fO N-A NO

0.5

10-SN-Agt•w

-4
040

Q30 10 20 30

Time (min)

Potential of platinum in solutions of silver ions.

References p. 474
 P. L. ALLEN, A. HICKLING 11 (2016)
analytically. The property of silver ions in catalysing thc oxidation of manganous
sulphate to permanganate by ammonium persulphate has been used to provide a
very sensitivc test for silver. It was found cxpcrimcntally that on boiling 2 drops

develop in the prescncc of silver ions at a concentration of approximately lo-c g

ion/litre. A sheet of platinum foil of IDO sq.cm arca •w•as wrapped in a loosc
spiral, and after cleaning 'evas cathodically polarized in IN sodium hydroxide
solution ; it was then washed and immersed in IN silver nitrate for 10 min. The
platinum was then withdrawn and washed repeatedly with distilled water until thc
washings gave no reaction for silver by the above test. When the platinum had
becn washed completely frec from silver ions, it was immersed in the reagent
mixturc so that the nitric acid present could dissolve any metallic silver on the
surface. The test solution was thcn boiled and an unmistakable pink coloration
developed. Repetition of the experiment with the platinum treated in different
ways showed that only such pretreatment as led to a reduction of thc surface and
a lowering of its potential would lead to a positive reaction for silver ; anodic
treatment of the platinum or cleaning it with hot concentrated nitric acid gave
negative results.
To obtain some quantitative idca of the amount of silver present, an
electrometric mcthod was used. A platinum electrode of 1 sq.cm area was
cathodically trcatcd in sodium hydroxide and was then anodically polarized in
0.1M potassium nitrate as electrolyte at a constant current of 10 microamp, its
potential relative to the reference electrode being measured on a valve-voltmeter
at various times so
vor„.

References 474
VOL. 11 (2016) PLATINUM INDICATOR ELECTRODE
that a charging curve could bc constructed. The cxperimcnt was then repeated
with the electrode aftcr it had bccn immersed in IN silver nitrate solution for ro
min. Thc charging curves are shown in Fig. 3, and it is at once apparent that after
irnmcrsion in silver nitratc thc electrode shows a well-defined arrest
corresponcling to the ionization of silver.
The quantity of clectricity passed in the
arrest is approximately 3500
microcoulombs corresponding to ca.
3.6•10-8 g atom of silver, or about atoms of
Age Taking the diarnctcr of thc silvcr atom
to be 2.6-10 "8 crn, thcrc would bc about
1.5•1015 atoms of Ag/sq.cm in a close-
packed monatomic layer. It is likely that thc
0.9
real arca of a platinum surfacc is
appreciably greater than its apparent arca,
and the ratio of the accessible to apparent
10 15 20 area has frequcntly bccn considcrcd'l to bc
Time (mul'
thick.
3. Anodic charging curves. Titration of cyanide. Titration of bromi- about
2. If this valuc is assumed to bc correct, thc amount of silver present
corrcspond to a layer some 7 ato:ns
des, iodidcs, and thiocyanatcs using t)lC
platinum indicator electrode gavc results very similar to those found with chloride.
The titration of potassiuln cyanide with silver nitrate is of interest,

References p. 474
 P. L. ALLEN, A. HICKLING 11 (2016)

since in thc initial stages of this Fig.

titration when the complex ion is being formed thc simple
Ag+ ion concentration is extremely IOW', and it was thought that thc platinum
elcctrodc might not herc respond to changes in silver ion concentration. In Fig.
4 arc shown some curves for the titration of 25 ml of 0.1M -0.2 potassium
cyanide with silvcr nitrate. Curvc is that obtaincd with a platinum
elcctrodc aftcr anodic P. polarization, and curvc 2 after clcaning 50
in warm concentrated nitric acid. ml A9NOJ added

Cathodically polarizcd platinum gave

curve 3, 'tvhilc 4. Potentiometric titration of cyanide.
471
curve 4 •.«vas that obtained using a silver indicator electrode. The jump of
potential at the first end-point is not very great with the platinum indicator
electrode, and it is decreased by oxidation of the platinum surface; it is clear that
in the early stages of the cyanide titration the platinum is unable to function
completely as a silver electrode even after the surface has becn subjected to
reducing treatment. A certain concentration of silver ions appears to bc necessary
before the platinum indicator electrode '.,vill respond, and this concentration is
higher when the platinum surfacc has been oxidized.
Other incrt electrodes. A gold electrode after cathodic polarization was found to
behave quite similarly to rcduccd platinum in silver nitratc/sodium chloride
titrations and gave results practically identical with those found using a silver
indicator clcctrodc; a typical titration curve is graph 1 in Fig. 5. If, however,
References 474
VOL. 11 (2016) PLATINUM INDICATOR ELECTRODE

11

1.0
2

0.9

05
05
04

03 10 20 30
4050 ml AgMOJ

Fig. 5. Potcntiomctric titration of chloride gold

indicator clectrode.

thc gold surfacc was oxidized by anodic polarization in acid solution, or by

trcatmcnt with wann concentrated nitric acid, curves 2 and 3 wcrc obtained. Hcre
the end-point is still indicated by a jump of potential, but all the potentials are in
a higher region of 0.9 to 1.1 v which is quite rcmovcd from the normal curve.
Electrodes preparcd from battery carbon and used without any pretreatment
other than washing with distilled water showed a jump in potential slightly after
the truc end-point in the titration had been reached, and thereafter gave potentials
similar to those found with a silver electrode. The general nature of these results
suggests that silver ions must be present in fairly considerable conccntrations
before carbon electrodes become responsive to them.
References p. 474
P. L. ALLEN, A. HICKLING 11 (1954)
472 VOL.

DISCUSSION

The cxpcrimcntal work has demonstrated that a reduced platinum surface on

immersion in a solution of silver ions becomes coated with metallic silver and
will then function as a silver electrode in argentometry. The formation of the
silver layer is not instantaneous and an appreciable although very low
concentration of silvcr ions is necessary for the reaction to take place. Any
pretreatmcnt which tends to oxidize thc platinum surface seems to increase both
thc time and concentration of silvcr ions which is required, so that a platinum
electrodc thus treated docs not function satisfactorily in the early stages of an
argentometric titration ; near the end-point, however, thc concentration of silver
ions is usually sufficiently great for some formation of silver to occur.
Thcsc obscrvations can bc interpreted in detail by reference to the potentials
manifcstcd by platinum after various types of pretreatment. Immediately after
cathodic polarization a platinum surface is likely to bc partly covered by
adsorbed hydrogen, and in neutral solution this is not lost until the potential is
more positivc than - 0.1 v4 . Thus, applying the Nernst equation, any solution in
which thc concentration of silver ions exceeds about 10 46 g ion per litre will tend
to react with a freshly cathodically reduced platinum surface liberating metallic
silver. Hence a cathodically polarized platinum electrode will behave as a silver
electrodc throughout almost any argentometric titration; only where the silver
ion concentration is extremely low, as for example in thc carly stages of the
titration of cyanide with silver nitrate, will it fail and even here the silver ion
concentration rapidly achieves a sufficicntly high value during the titration for
silver formation to occur on the metal surfacc. A platinum surface which has
been mildly oxidized is likely to bc covcred with platinous oxide, and the Pt/PtO
potcntial in ncutral solution is ca. + 0.5 v4 ; such a surface will tend to reduce
any solution in which the silver ion concentration exceeds about 10-6 g ion per
litre. Thus such a surface will not be responsive to silver ions in the early stages
of many argentomctric titrations and the potential will remain steady in the
vicinity of the oxide potential. At or near the end-point, however, the silver ion
concentration will rise sufficiently for silver to be formed on the platinum
surface, and from this point onwards the electrode will behave as a silver
electrode. This agrees closely with what has been observed. Drastic oxidation of
the platinum surface may lead to the formation of platinic oxide, and the Pt/Pt02
References p. 474
VOL. 11 (2016) PLATINUM INDICATOR ELECTRODE
5
potential is ca. + 0.6 v in neutral solution. In this case again the platinum surface
will not respond to changes in silver ion concentration while this remains low,
and the potential will remain close to + 0.6 v in an argentometric titration in
neutral solution ; whcn the silver ion concentration reaches about 10-3 g ion per
litre, as for example at the end-point, the platinum will again simulate a silver
indicator electrode.
Similar considerations would seem to apply to other inert electrodes. Where the
potential of the surface after pretreatment is sufficiently low relative to the
473
standard silver potential, then the electrode will become coated with metallic
silver in the early stages of a titration and will function throughout as a silver
electrode. If the potential of thc surface is not low enough initially, the end-point
may be reached or even slightly passed before the potential of the electrode varies
with the silver ion concentration. With a sufficiently strongly oxidized surfacc the
possibility exists that its potential may be so high that no reduction of the silver
ions will occur at any stage in the titration. In this connexion the behaviour of
gold after anodic polarization or treatment with warm conccntratcd nitric acid is
of particular interest. Hcrc the potential throughout a chloridc titration is much
higher than the standard silvcr potential (sec Fig. 5) but the end-point is still
indicated by a small jump of potential. After drastic oxidation a gold surfacc is
likely to bc covered by auric oxide, and the Au/Au203 potential in neutral solution
is ca. -L 1.0 vo ; it is notcworthy that thc titration curves for the oxidized gold
electrode lie between 0.9 and 1.1 v. The small jump of potential of ca. 0.1 v at the
end-point indicates that some species in equilibrium with silver ions must be
formed on the gold surface, and it seems not unlikely that this might be a peroxide
of silver produced by the action of auric oxide on silver ions. In support of this
view a platinum electrode was anodically polarized in o. IN silver nitrate so that
it became coated with a black deposit which is usually considered to contain a
peroxide of silver? ; the clectrodc was then washed and used as an indicator
electrode in thc titration of 0.1 N sodium chloride with 0.1 N silver nitrate. The
titration curve obtained was somev„'hat similar to that observed with oxidized
gold; it lay between 1.1 and 1.3 v, there being a small jump of about 0.15 v at the
cnd-point of the titration.
References p. 474
P. ALLEN, A. HICKLING 11 (2016)
SUMMARY
A study has been made of the behaviour of platinum and some other inert elcctrodes
in silver nitrate titrations. Where the metal surface has been subjected to a reducing
treatment, such as cathodic polarization, before use, thc electrode. will often function as
a silver indicator electrode throughout the titration. It has becn shown experimentally
that this is due to the formation of a layer of metallic silver upon the electrode by
interaction of the surface with silver ions in solution. If the metal surface undergoes such
pretreatment that it is oxidized, then its potential normally remains at the oxide value
during a silver nitrate titration until the silver ion concentration is sufficiently great for
this value to be exceeded by the silver/ silver ion potential; formation of metallic silver
then again takes place and from this point onwards the electrode behaves as a silver
electrode. A detailed interpretation of the behaviour of platinum after various
pretreatments has been made along these lines.
RÉSUMÉ
Une étude a été effectuée sur le comportement du platine et de quelques autrcs
électrodes inertes lors des titrations au nitrate d 'argent. Lorsque la surface métallique a
été soumise à un traitement de réduction, tel que la polarisation cathodique, avant
utilisation, I'électrode fonctionnera comme électrode indicatrice d 'argent dans tout le
cours de la titration. Il a été prouvé expérimentalement que ceci est d Ci à la couche
d'argent métallique qui se forme sur l'électrode, par interaction entre 474 C.
VOL.
sa surface et Ics ions argent de la solution. Dans le cas où la surface du métal est
soumise à un traitcmcnt préliminaire d'oxydation, son potentiel conserve normalement
la valeur de celui de l'oxyde, pendant la titration au nitrate d'argent, et cela juqu'au
momcnt où la concentration des ions argent devient suffisamment forte pour que cette
valeur soit dépasséc par le potentiel Ag/Ag+; à partir de ce moment, il y a de nouvcau
formation d'argent métallique et l'électrode se comporte alors comme électrodc
d'argcnt.
Dans cct article, les auteurs ont donné unc interprétation détaillée clu comportcmcnt
du platine ayant subi différcnts traitcments préliminaires.
VOL. 11 (2016) PLATINUM INDICATOR ELECTRODE
ZUSAMMENFASSUNG
Es wird (las Vcrhaltcn von Platin und einigen andern Edel:nctallelektroden bei clen
Titrationcn mit Silbcrnitrat untcrsucht. Sofern die Mctallobcrfliiche einer
recluzicrcnden Behancllung unterzogcn wurde vor der Verwendung, Wie z. B. einer
kathoclischcn Polarisation, funktionicrt die Elektrodc als Silberindikatorelektrode
währcnd des ganzen Titraiionsvcrlaufes. Es wurde experimentell bewiesen class dies
von clcr metallischcn Silberschicht herrührt, welche Sich auf der Elektrode bilclct, und
zwar durch die Gcgcnwirkung der Oberfläche mit dcn Silberionen der Lösung. Sofern
dic Mctalloberfláche ciner oxydierenden Vorbehandlung unterzogen wurde, bchält ihr
Potcntial den Wert des Oxydes währcnd der Titration mit Silbernitrat, und zwar solange
bis die Konzcntration an Silbcrionen gross genug wird, urn (licsen Wert zu il
berschreiten (lurch clas Potcntial Ag/Ag+. Von diese:n Augenblick an bildct Sich
wiedcr inetallischcs Silbcr und die Elektrode vcrhält Sich clann Wic einc
Silbcrclcktrodc. In dicscr Arbcit geben dic Autoren einc dctaillierte Intcrprätation dcs
Vcrhaltcns von Platin, welches verschiedenen Vorbehandlungen unterzogcn wurde.
REFERENCES
1 E. MÜLLER, Z. Elektrochem., 30 192,1) 420.
F. SIERRA ANI) O. CARPENA, Ana es real soc. esÞan. fis. y qu'm. (Madrid), 46B
(1950) 547, 627 ; Pubs. inst. quim „Alonso-Btwba", 4 (1950) 291.
J. M. BATIIER AND J. P. RILEY, J. Cons. intcrn. ExPloration MC", 18 (1953) 277.

A. HICKLING, Tgans. Faraday Soc. , 41 (1945) 333.

G. GRUBE, Z. Ele/etrochcm., 16 (1910) 621.
0 A. HICKLING, Trans. Faraday Soc. , 42 (1946) 5 J 8.
7 Sec A. HICKLING AND D. TAYLOR, Faraday Soc. Discussion, 1 (1947) 277.

Receivcd April 26th, 1954

References p. 474