Talanta. 1960, Vol. 7. pp. 51 to 55. Pcrgamon Press Ltd.

Printed in Northern Ireland

FUNDAMENTAL PRINCIPLES OF TITRATIONS WITH

POTASSIUM BROMATE

(Received 20 June 1960)

~~-~s~ on the results ofresearches into the chemistry and analytical uses of interhalogen
compounds and of halogen ions of one positive charge, the fundamental principles of bromatometry
are discussed by the authors.
It is pointed out that in redox titrations with patassium bromate, in place of bromate or bromic
acid, actually elementary bromine, or bromine chloride, or bromine chloride and elementary chlorine
act as agents. Thus, bromine and bromine chloride form a complex with the halide content (bromide
and chloride, respectively) of the solution to be titrated. The redox potential and polarity (eiectro-
philic nature] of this complex can be cc&roiled by varying #heh&de concent&o~.
By clearingup the fundamentalprinciplesit AasbeenpossiMeto d&e&e preciselythe optimum
experimentalconditions of the various bromatometricprocedures.

THE conventional

BrCl + 2C1, -I- 3H,O (4)

Thus, in presence of to
equation in the presence of of bromide (when the
ratio of to bromide is 1: 21, to equation
In the absence of is present, bromine chloride
elementary chlorine2 to equation the given conditions,
therefore, or bromine chloride:, or of bromine
chloride and elementary chlorine act oxidising agents in
The direct oxidising effect of bromate in a medium
and bromide and the bromide the
reduction process are bound by (as poorly dissociated mercuryrr
ta prevent the formation of bromine. by bromate alone
are extremely can only be for analytical purposes in
in the presence of and a rule solely in hot
5I
52 E. SCHULEK,K. BURGER and J. LASZLOVSZKY

solutions.* In the conventional bromatometric titrations (generally carried out

in solutions containing bromide or hydrochloric acid) the course of the reaction
is determined rather by that of the redox systems bromine/bromide or bromine
chloride~bro~de and chlo~ne~chlo~de instead of by the redox potential of the system
bromate/bromide or of the system bromate/bromine (see Table I).

Redox potential,
System
V

BrO,-/Br, 1.52
BrO,-/Br- 1.42
I% ABr- 1.087
BrQ eomplex/Br- 1.3
CI, ss/Cl- 1.36

One should also consider that in aqueous solutions containing halides, both
elementary bromine and bromine chloride and, to a smaller degree, also elementary
chlorine, are present as halide complexes. The redox potentials of halogen-halide and
interhalogen-halide complexes are below those of the corresponding free halogens and
interhalogens, and decrease with a rise in the halide concentration.4
Further, we must emphasise that in a great number of reactions which serve as a
basis of bromatometric determinations, particularly in oxidation reactions of organic
compounds, in halogen substitution reactions of aromatic molecules, in halogen
addition reactions of unsaturated double bonds etc., the chemical process is not
determined solely by the redox potential of the reaction partners, because
their structure and chemical nature also play a decisive role. Thus, the
bromine substitution5 of aromatic compounds of nucleophilic nature and the
halogen addition6 of unsaturated double bonds of similarly nucleophilic nature take
place with bromine chloride (electrophilic in nature) at rates markedly exceeding those
of the reaction with less polar (i.e. less electrophilic) elementary bromine or with
elementary chlorine of higher redox potential but similarly of less electrophilic nature.
However, the formation of halogen-halide and interhalogen-halide complexes
(under the action of halide ions) also reduces the degree of polarity and thus the
electrophilic nature of halogens and interhalogens in addition to the redox potential of
the system proper.
It is possible in this way, by varying the concentration of bromide according to
the nature of the substance to be determined and to the requirements to be met during
the determination, to choose whether elementary bromine developed according to
equation (2), or bromine chloride according to equation (3) or bromine chloride and
elementary chlorine according to equation (4) should constitute the active agent.
Further, the redox potential of the bromine-bro~de complex and the polarity of the
molecule will also be determined by the bromide concentration, while the redox
potential and polarity, together with the electrophilic nature of the bromine chloride-
chloride complex can be governed by varying the chloride concentration.
* There is no possibility of oxidising even ascorbic acid to dehydro-ascorbic acid if the conditions ex-
clude the formation of elementary bromide and bromine chloride. A bromine addition before oxidation
was observed by Schulek, Kovhcs and R&sa.“’
 Titrations with potassiumbromate 53

Taking into account the above considerations, the phenomenon which was pointed
out by Ziillner and Varga,’ without an attempt at explanation, can be interpreted. Thus,
in a great number of bromatometric procedures, an increase in the bromide concen-
tration gives markedly lower (3 to 50%) results. In other cases, however (such as
antipyrinea), more precise determinations are possible at higher bromide concentrations,
while in the presence of too small an amount of bromide, the results are too high due
to over-bromination. Finally, in certain cases (such as with hydrazines or hydroxyl-
amine?, the determinations must be carried out in a hydrochloric acid medium free
from bromide.
On increasing the bromide content of a reaction mixture, according to the afore-
mentioned considerations, complexes form and the dissociation of the complexes is
suppressed. Thus, the redox potential, together with the polarity (electrophilic nature)
of bromine are reduced. This is the reason why the rate of oxidation and, in certain
cases, that of bromination, respectively, decrease and low results are obtained. In
contrast, in the bromatometric determination of molecules which, on reacting with
agents of higher redox potential and more electrophilic nature, may suffer an un-
desirable over-bromination or may lead to undesired side reactions, the presence of an
agent of lower redox potential and lower reactivity can be attained by using excess
bromide. Finally, bromine chloride (formed in a hydrochloric acid solution free from
bromide or, alternatively, containing given amounts of bromide, e.g. 1:2 ratio of
BrOa-: Br-) is necessary in certain determinations where quantitative oxidation is to be
conducted in a given manner. Also, in the halogen addition of unsaturated double
bonds where the reactivity is hindered by negative substituents of the vicinal carbon
atoms, bromine chloride should be used.
During the preparation and practical use of a standard solution of bromine
chloride suitable for analytical purposes, we succeeded in proving completely the
validity of the afore-mentioned presumptions. The standard solution of bromine
chloride was prepared according to equation (3) in a hydrochloric acid medium from
equivalent amounts of bromate and bromide. l Careful physical and chemical
investigations (absorption spectra in the visible and ultraviolet regions, redox poten-
tials, various chemical reactions, etc.) were carried out to prove that the solution
obtained is, in all respects, identical to the bromine chloride solution containing
hydrochloric acid which was prepared from elementary bromine and chlorine.
The bromine chloride substitution of a great number of aromatic compounds,10
the addition of bromine chloride to unsaturated double bondWP and many
oxidation reactions with bromine chloride2J21f3215were subjected to a thorough
examination. In all cases, as expected, a marked increase of reaction rates was
observed.
The standard solution of bromine chloride suggested by us was applied with
success to the determination of reducing substances which can be oxidised only
extremely slowly or non-stochiometrically by elementary bromine. The bromato-
metric determination of these substances was previously only possible in media free
from bromide, in solutions of high hydrochloric acid concentration. In contrast to
that, we were able to determine hydrazine and its derivative@ in an aqueous solution
directly, without acidification, by using bromine chloride, whilst the method suggested
by Kurtenacker yields correct results only in solutions of hydrochloric acid content
over 10%. Bromine chloride was similarly used with success in the determination of
hypophosphite12 and hydroxylamine.2
54 E. SCHULEK, K. BURGER and J. LASZLCWSZKY

On using a standard solution of bromine chloride, it was possible to determine

unsaturated compounds as well, e.g. maleic acid and fumaric acid,6 which otherwise
are practically incapable of taking up bromine in an addition reaction in an acidic
medium, due to the hindering effect of the carboxylic groups on both carbon atoms
in the vicinity of the double bond.
The investigation of aromatic substitution reactions by bromine chloride
disclosed markedly higher reaction rates in these reactions than in the substitution
reactions by elementary bromine. However, on applying bro~nation periods longer
than the optimum values, as is usual in the Koppeschaar method, the obtained results
were high, pointing to oxidative side reactions. Similar phenomena were observed
when measurements were carried out in the presence of minute amounts of bromide
(or in solutions free from bromide) according to Koppeschaar.
Considering the higher reaction rates of brominations carried out with bromine
chloride and with Br+ cations developed du~ng the dissociation of this compound,
respectively, it was possible to interpret the mechanism of action of mercuryIf ions
i.e. of the “catalyst” generally used in bromine addition reactions14
Thus, it was assumed that the heterolytic dissociation of elementary halogen is
completed by mercuryrr ions, with the formation of poorly dissociated mercury11
halides :
Hg2+ + Br, -+ HgBrt + Br+ (5)
The increase in reaction rate is due to the formation of Br+ cations.
In order to prove the validity of this assumption, bromine water was treated with
mercury11 chloride and, since HgBrCl is less dissociated than HgC12, bromine chloride
should be formedzl according to the equation:

HgCl, + Br, -3 HgBrCl + BrCl.

Bromide chloride could, in fact, be distilled off, then identified by its ultraviolet
spectrum and by chemical reactions.
In this way, researches into the chemistry and analytical use of interhalogen
compounds and of halogen ions of one positive charge resulted in a clearing up of the
fundamental principles of bromatomet~. With a complete knowledge of the chemical
processes occurring during the determination and of the ways of controlling them, it was
possible to establish precisely the optimum conditions for the various bromatometric
procedures.

~-Die Gnmdlagen der Bromatometrie werden diskutiert. Es wird gezeigt, dass in

Redoxtitrationen unter Verwendung von Kaliumbromat an Stelle von Broms&ue eJementares Brom,
Bromchlorid oder Bromchlorid und elementares Chlor die reagierenden Komponenten sind. Brom
und Bromchlorid bilden einen Komplex mit dem Halogen (Bromid oder Chlorid) der zu titrierenden
Losung. Redoxpotential und Polaritat (Elektrophihe) dieses Komplexes kann durch Regulierung
der Halogenkonzentration geiindert werden. Auswertung experimenteller Befunde machte es
moglich die optimalen Bedingungen fiir verschiedene bromatometrische Bestimmungen zu ermittem.

R&um&Les principes de la bromatometrie sont discut6s. Les auteurs font remarquer que, dans Ies
titrages par oxydo-reduction utilisant le bromate de potassium au lieu de l’acide bromique, le brome
elementaire, ou le chlorure de brome, ou le chlorure de brome et le chlore elementaire agissent comme
reactifs. Le brome et le chlorure de brome ferment un complexe avec l’halogenure (bromure et
chlorure) de la solution B titrer. Le potentiel d’oxydo-reduction et la polarite (nature electrophite) de
 Titrations with potassium bromate 55

ce complexe peuvent &e control& en faisant varier la concentration d’halogkmre. L’examen des
conditions experimentales a permis de determiner les conditions experimentales optimales pour les
differentes techniques bromatometriques.

REFERENCES
1 E. Schulek and K. Burger, Tafu~a, 1958,1,219.
* K. Burger, F. Gaizer and E. Schulek, ibid., 1960, 5, 97.
8 J. Laszlovszky, Annales Univ. SC. Eitvijs, in press; J. Laszlovszky and E. Schulek, Acta Pharm.
Hung., 1959,29,217.
4 E. Pungor, K. Burger and E. Schulek, Magyar Kim. Folyoirat, 1959,65, 301; J. Znorg. Nuclear
Chem., 1959,11, 56.
5 E. Schulek and K. Burger, Z’a~anfu, 1958, 1, 224.
8 Zdem, Z. analyt. Chem., 1960,172,98.
’ E. Zbllner and E. Varga, Actu Chim. Acad. Sci. Hung., 1957,12,1.
a A. Kurtenacker and J. Wagner, Z. anorg. Chem., 1922,120,261.
s A. Kurtenacker and R. Neusser, ibid., 1923,131, 27.
lo E. Schulek and K. Burger, Tulunfu, 1958, 1, 147.
r1 Zdem, ibid., 1960,7,46.
I* K. Burger and L. Lad&nyi, Acta Pharm. Hung., 1960,30, 80.
Is E. Schulek and K. Burger, Talanta, 1958, 1, 344.
l4 Zdem, ibid., 1960,7,41.
I6 J. Laszlovszky, Pharm. Zentralhalle, in press.
lo K. Burger, E. Schulek and L. Ladanyi, Acta Pharm. Hung., 1959, 29,241.
I7 E. Schulek, J. Kovacs and P. R6zsa, Z. analyt. Chem., 1941, 121,18.