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Rebrov A 2009
Rebrov A 2009
PHYSICAL CHEMISTRY
OF SOLUTIONS
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 oxygencontaining 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 oxygencontain
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 right. We must therefore estimate the content of oxy
preparation of optical materials extensively used in gencontaining impurities in KBr to introduce correc
modern science and technology. These are largely KBr tions into the composition of charge mixtures taking
single crystals used to manufacture windows for infra into account the precipitation of rareearth metal
red instruments. K2LaBr5 single crystals activated by и oxides. The content of oxo anions in initial KBr is as a
Ce3+ ions (K2La1 – xCexBr5) are a promising scintilla rule lower than in melt because of the presence of
tor, whose technical characteristics excel those of organic impurities, which decompose to release water
broadly used NaI : Tl [1]. and СО2 when the initial salt is heated. This results in
Fairly stringent requirements are imposed on the the pyrohydrolysis of KBr according to the scheme
purity of halide materials for optics, because the pres
ence of impurities negatively influences the functional 2KBr + H2O↑ + CO2↑ K2CO3 + 2HBr↑ (5)
characteristics of end products. For instance, the pres
2– 2– and the appearance of some additional amount of oxy
ence of oxygencontaining impurities ( CO 3 , SO 4 )
gencontaining impurities in melts compared with
causes the appearance of absorption bands in the IR unmolten potassium bromide.
range. As far as the K2La1 – xCexBr5 compound is con
cerned, it is prepared from a melt with the composi The purpose of this work was to study the behavior
tion 2KBr + (1 – x)LaBr3 + xCeBr3, and the presence of anionic oxygencontaining impurities in a KBr melt
of oxygencontaining impurities in KBr results in the potentiometrically with the use of a Pt(O2)|YSZ oxygen
precipitation of La2O3 and CeO2 when the salt mixture electrode (YSZ is a membrane on the basis of ZrO2 sta
melts, bilized with 10 mol% Y2O3) and develop a method for
estimating the total concentration of oxo anions in this
2La3+ + 3O2– La2O3↓, (1) melt.
Ce3+ + 2O2– – e CeO2↓. (2) The behavior of oxygencontaining impurities is
This causes composition deviations from stoichiome described in terms of the Lux–Flood definition,
try. О2– ions appear in melts because of the dissocia according to which an acceptor of oxide ions is an
tion of oxygencontaining impurities, acid, and a donor of O2– is a base [2]; that is,
2–
CO 3 O2– + CO2↑, (3) Acid O2– Base. (6)
2–
SO 4 O2– + SO3↑. (4) By this definition, metal cations (Eqs. (1) and (2)),
CO2 (Eq. (3)), and SO3 (Eq. (4)) are acids, and metal
The precipitation of oxides according to reac 2– 2–
tions (1) and (2) shifts equilibria (3) and (4) to the oxides, CO 3 , and SO 4 are bases.
1879
1880 REBROVA et al.
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 oxygencontaining 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
stepwise 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