ISSN 0036
0244, Russian Journal of Physical Chemistry A, 2009, Vol. 83, No. 11, pp. 1879–1882.

© Pleiades Publishing, Ltd., 2009.

Original Russian Text © T.P. Rebrova, V.L. Cherginets, T.V. Ponomarenko, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 11, pp. 2068–2071.

PHYSICAL CHEMISTRY
OF SOLUTIONS

A Study of Lux–Flood Acid
Base Reactions in KBr Melts at 800°C

T. P. Rebrovaa, V. L. Cherginetsb, and T. V. Ponomarenkoa
a
Institute of Scintillation Materials, National Academy of Sciences of Ukraine, Kharkov, Ukraine
b
National Technical University “Kharkov Polytechnical Institute,” Kharkov, Ukraine
e
mail: inorg@isc.kharkov.com
Received July 1, 2008

2–
Abstract—The dissociation of CO 3 (pK = 2.4 ± 0.2) and precipitation of MgO (pLMgO = 10.66 ± 0.1) in a
KBr melt at 800°C were studied potentiometrically with the use of a Pt(O2)|ZrO2|(Y2O3) membrane oxygen
electrode. The direct calibration of the electrochemical circuit allowed only the equilibrium concentration of
O2– (of strong bases) to be determined in the melt. The total concentration of oxygen
containing impurities,
2– 2–
including CO 3 and SO 4 weak bases, can be found by the potentiometric titration of a sample of KBr by
adding MgCl2 (Mg2+), a strong Lux–Flood acid, which causes the decomposition of these oxygen
contain

ing anions. This reaction can also be used to remove oxo anions from alkali metal halide melts.
DOI: 10.1134/S0036024409110120

Potassium bromide is the initial compound for the
preparation of optical materials extensively used in
modern science and technology. These are largely KBr
single crystals used to manufacture windows for infra

red instruments. K2LaBr5 single crystals activated by и
Ce3+ ions (K2La1 – xCexBr5) are a promising scintilla

tor, whose technical characteristics excel those of
broadly used NaI : Tl [1].
Fairly stringent requirements are imposed on the
purity of halide materials for optics, because the pres

ence of impurities negatively influences the functional
characteristics of end products. For instance, the pres

2– 2–
ence of oxygen
containing impurities ( CO 3 , SO 4 )
causes the appearance of absorption bands in the IR
range. As far as the K2La1 – xCexBr5 compound is con

cerned, it is prepared from a melt with the composi

tion 2KBr + (1 – x)LaBr3 + xCeBr3, and the presence
of oxygen
containing impurities in KBr results in the
precipitation of La2O3 and CeO2 when the salt mixture
melts,
2La3+ + 3O2– La2O3↓,
Ce3+ + 2O2– – e CeO2↓.
This causes composition deviations from stoichiome

try. О2– ions appear in melts because of the dissocia

tion of oxygen
containing impurities,
2–
CO 3 O2– + CO2↑,
2–
SO 4 O2– + SO3↑.
The precipitation of oxides according to reac

tions (1) and (2) shifts equilibria (3) and (4) to the
right. We must therefore estimate the content of oxy

gen
containing impurities in KBr to introduce correc

tions into the composition of charge mixtures taking
into account the precipitation of rare
earth metal
oxides. The content of oxo anions in initial KBr is as a
rule lower than in melt because of the presence of
organic impurities, which decompose to release water
and СО2 when the initial salt is heated. This results in
the pyrohydrolysis of KBr according to the scheme
2KBr + H2O↑ + CO2↑ K2CO3 + 2HBr↑ (5)
and the appearance of some additional amount of oxy

gen
containing impurities in melts compared with
unmolten potassium bromide.
The purpose of this work was to study the behavior
of anionic oxygen
containing impurities in a KBr melt
potentiometrically with the use of a Pt(O2)|YSZ oxygen
electrode (YSZ is a membrane on the basis of ZrO2 sta

bilized with 10 mol% Y2O3) and develop a method for
estimating the total concentration of oxo anions in this
(1) melt.
(2) The behavior of oxygen
containing impurities is
described in terms of the Lux–Flood definition,
according to which an acceptor of oxide ions is an
acid, and a donor of O2– is a base [2]; that is,
(3) Acid O2– Base. (6)
(4) By this definition, metal cations (Eqs. (1) and (2)),
CO2 (Eq. (3)), and SO3 (Eq. (4)) are acids, and metal
2– 2–
oxides, CO 3 , and SO 4 are bases.

1879
1880 REBROVA et al.

E, V (dependence 2) corresponds to the classic reversibility

0.2 of the oxygen electrode according to the equation
3 1
(1/2)O2↑ + 2e O2– (9)
0.1
and the “peroxide” function of the oxygen electrode,
2– 2–
0 ( 1/2 )O 2 + e O , (10)
respectively. A detailed explanation of such a behavior
−0.1
2 of the Pt(O2)|YSZ electrode can be found in [5, 6].
These dependences were used to calculate pO from
−0.2 EMF values. For instance, the EMF of circuit (7) in
pure KBr melt (0.240 V) can be used to estimate the
−0.3 equilibrium concentration of О2–, 2 × 10–5 mol/kg.
This value is difficult to use for extracting any informa

0 2 4 tion about the content in the melt of oxo anions,
−logm0O2− which are weak Lux–Flood bases. In addition, the dis

2–
sociation constant of CO 3 in alkali metal halide
Fig. 1. Dependence of EMF (E) of circuit (5) on the initial
concentration of the donor of oxide ions in KBr melt at melts can change very substantially. We cannot there

800°С, (1, 2) in argon atmosphere (pO = – log m
0 fore from purely general considerations answer the
2– ) and
O question of whether the presence of O2– in a pure KBr
(3) in СО2 atmosphere. melt is caused by carbonate dissociation or carbonate
dissociation by Eq. (3) is suppressed under these con

The circuit for electromotive force (EMF) mea
ditions.
surements was To study the dissociation of carbonate ions in KBr
melts, we calibrated circuit (7) in the atmosphere of
+ СО2 (Fig. 1, dependence 3). It follows from Fig. 1 that
Pt Ag 0.1 mol/kg Ag ( AgBr ), the introduction into the melt of СО2 instead of argon
(7)
KBr||KBr + O
2–
YSZ Pt ( O 2 ). causes a substantial increase in the EMF as a result of
equilibrium shift to the left in reaction (3). The data
Circuit (7) was calibrated in argon by adding strong obtained allowed us to estimate the dissociation con

stant of carbonate ions in KBr melts at 800°С (an
base NaOH, which, in a dry atmosphere, fully dissoci
example is given in Table 1), it was found to be pK(3) =
ated in melts according to the equation [3, 4] 2.4 ± 0.2, K3 = 4 × 10–3 (P = 0.95, n = 8). The obtained
2OH– O2– + H2O↑. (8) constant of equilibrium (2) led us to conclude that, in
the atmosphere of argon of os. ch. (special purity)
grade (the content of СО2 at a level of 10–2–10–3 vol %),
The dependence of EMF on pO (pO ≡ – log a O2– ≈ 2–
the degree of CO 3 dissociation was within the inter

– log m O2– , where a O2– and m O2– are the activity and val 40–80%. It follows that, because of the incomplete
2–
molality of oxide ions in a melt) was typical of the dissociation of CO 3 , the equilibrium concentration
Pt(O2)|YSZ electrode in melts of alkali metal halides of О2– in pure KBr is lower than the sum of the initial
(Fig. 1). The presence of two linear regions with slopes 2–
concentrations of O2– and CO 3 .
close to 1.15 RT/F (dependence 1) and 2.3 RT/F As regards another impurity frequently present in
2–
alkali metal halides, SO 4 , this is a very weak base and
2–
Table 1. Data on the dissociation of CO 3 in KBr melt at it cannot be detected by direct potentiometric mea

800°C surements [7]. For this reason, it should be determined
by an indirect method. It is known that strong acids
–log m O2–
0
Е, V рО pK(2) decompose sulfate ions in melts [8]. The magnesium
cation can be such an acid; it is introduced into melts
1.94 0.180 4.25 2.31 in the form of magnesium halide. The total reaction
equation has the form
1.19 0.120 3.7 2.51
2–
0.91 0.075 3.28 2.37 Mg2+ + SO 4 MgO↓ + SO3↑. (11)
0.59 0.050 3.06 2.46 This reaction is additionally convenient in practice
0.45 0.020 2.78 2.33 because all its products are removed from melts in the

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 11 2009

 A STUDY OF LUX–FLOOD ACID
BASE REACTIONS 1881

E, V E, V
1
(a) 0.6 (b)
2

0.4
0.5

0 0.4

0.3
0.4

0.2
0 0.05 0 0.002 0.004
m0O2− m0Mg2+

Fig. 2. Potentiometric titration curves in KBr melt at 800°C: (a) Mg2+ (MgCl2, 3 × 10–2 mol/kg) + О2– (titrant) and (b) pure
KBr ((1) 150 and (2) 50 g) + MgCl2 (titrant).

form of gas and precipitate. To use this reaction for the concentration of oxo anions destroyed by Lux–
determining the content of sulfate ions, we must pre
Flood acids can be estimated at 7.5 × 10–4 mol/kg,
liminarily estimate the solubility of MgO in this melt. which is almost 40 times higher than the equilibrium
We performed such a study by the method of potenti

ometric titration with a strong base NaOH. Titration is concentration of О2– in a pure KBr melt.
accompanied by the reaction The suggested method for estimating the concen

2+ 2–
Mg +O MgO↓, tration of oxygen
containing impurities can have
(12) practical applications for purifying alkali metal halide
pL MgO = – log ( m Mg2+ m O2– ),
melts from oxo anions. Indeed, the data obtained can
where pLMgO is the MgO solubility index. be used to calculate the amount of magnesium halide
The dependence of EMF on the initial titrant necessary for the complete decomposition of oxo
molality is shown in Fig. 2a, and data processing anions in melts. The solubility of magnesium oxide in
results are summarized in Table 2. The potentiometric melts is less than 10–5 mol/kg. Because of a difference
titration curve is characteristic of oxides almost insol
in density (3.58 g/cm3 for MgO and 2.75 g/cm3 for
uble in melts [9]. The tabulated data can be used to
KBr [10]), it settles down on the bottom of a crucible,
estimate the solubility product of MgO in KBr melt,
pLMgO = 10.66 ± 0.1 (P = 0.95, n = 6). Such a small sol
which is especially convenient for growing single crys

ubility product value makes it possible to use Mg2+ for tals according to Chokhral’skii.
the complete removal of oxo anions from melt if it is
introduced in the concentration equivalent to that of
Table 2. Data on the solubility of MgO in KBr melt at 800°C
these impurities.
The total content of oxo anions in KBr melt was 0
m O2– , mol/kg Е, V рО pLMgO
determined by the titration of various initial KBr sam

ples with MgCl2. The corresponding EMF depen
0.0006 0.674 9.15 10.64
dences on the initial titrant (MgCl2) molality are
shown in Fig. 2b. The two potentiometric curves 0.0025 0.670 9.11 10.63
almost coincide. The initial potentiometric curve 0.0053 0.672 9.13 10.69
region corresponds to EMF in pure melt, the addition 0.0102 0.663 9.05 10.69
of Mg2+ causes a sharp increase in EMF because of the 0.0195 0.635 8.79 10.66
formation of SO3 acid in reaction (9), but the acid is 0.0219 0.624 8.69 10.64
removed from the melt with time by an argon flow, and
EMF shifts to its value for the pure melt. After the 0.0283 0.586 8.34 10.67
2– 0.0336 –0.220 2.50
complete decomposition of SO 4 , EMF changes
0.0371 –0.321 2.06
step
wise at the point corresponding to the complete
decomposition of this weak base, because the melt 0.0429 –0.415 1.66
contains excess Mg2+ acid. It follows from Fig. 2b that 0.0506 –0.463 1.45

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 83 No. 11 2009

1882 REBROVA et al.

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