ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2008, Vol. 53, No. 9, pp. 1509–1511. © Pleiades Publishing, Ltd.
, 2008.
Original Russian Text © A.S. Basin, A.B. Kaplun, A.B. Meshalkin, N.F. Uvarov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 9, pp. 1611–1613.
PHYSICOCHEMICAL ANALYSIS
OF INORGANIC SYSTEMS
The LiCl–KCl Binary System
A. S. Basina, A. B. Kapluna, A. B. Meshalkina, and N. F. Uvarovb
a
Institute of Thermal Physics, Siberian Branch, Russian Academy of Sciences,
pr. akademika Lavrent’eva 1, Novosibirsk, 630090 Russia
b Institute of Solid-State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences,
ul. Kutateladze 18, Novosibirsk, 630128 Russia
Received July 10, 2007
Abstract—Liquidus temperatures in the LiCl–KCl system in the composition range from 0 to 100 mol % KCl
have been measured for 16 samples using the methods of oscillation phase analysis and thermal analysis. The
melting points of the components and the eutectic composition of the system have been refined.
DOI: 10.1134/S003602360809026X
In recent years, the eutectic of the lithium chloride– RESULTS AND DISCUSSION
potassium chloride binary system attracts more atten- The results of measurements are presented in the
tion as a low-temperature and low-viscosity electrolyte table and in figure. By our data, the eutectic melts at
for electric power cells and for refining metals [1, 2].
The LiCl–KCl system was studied experimentally at
the beginning of the 20th century [3, 4] and later [5–9] Temperatures of phase equilibria in the LiCl–KCl system
as part of ternary and quaternary chloride systems.
Fairly large differences were observed both in the melt- Composition,
tL (LiCl), °C tE, °C tL (KCl), °C
ing point (from 348 [7] to 360°ë [8]) and in the eutectic mol % KCl
composition (from 40.5 [3] to 42.5 [5] mol % KCl).
0 607
EXPERIMENTAL 10 568 353
We carried out measurements on 16 samples in the 20 512 352
composition range from 0 to 100 mol % KCl. Phase 29 452 352
transformations of the system were studied on an
experimental setup combining oscillation phase analy- 34.9 416 352
sis (OPA) [10–12] and thermal analysis (TA). Samples
30–40 g in weight were prepared from starting reac- 39.9 371 352
tants (lithium chloride monohydrate and potassium
41.4 357 352
chloride of special purity grade) preliminary dried at
150–200°ë for 2–3 h. In the measuring cell, we used a 42 – 352 357
platinum crucible 45 mm in diameter and 50 mm in
height. The melt height was ~30 mm. To prevent segre- 45 – 352 390
gation, samples after melting were stirred via nitrogen
bubbling. 45.1 – 352 392
The sample temperature was measured using a 50 – 352 454
Pt−Pt/Rh thermocouple in a platinum case immersed 60 – 353 553
into the melt to a depth of ~20 mm. DTA curves were
recorded using an N-307 x, y recorder at a heating rate 70 – 351 631
of 5 K/min.
80 – 352 688
The measurement error of the liquidus temperature
and melting points was ±2°ë K [10]. Pt–Pt/Rh thermo- 89.91 – 350 736
couples were calibrated at the Novosibirsk Institute of
Metrology. 100 – – 774
1509
1510 BASIN et al.
T, °C
1 774
2
700
607
600
500
400
E 352
LiCl 20 40 60 80 KCl
mol %
Phase diagram of the lithium chloride–potassium chloride system: (1) OPA data and (2) TA data. Regions of solid solutions near
the components are not shown.
352°ë and contains 41.8 mol % KCl and 58.2 mol % perature control system and redistribution of thermal
LiCl. The melting points of lithium chloride (607°ë) fluxes in the DTA setup or with considerable impurity
and potassium chloride (774°ë) coincide with data in levels in the sample. For example, our KCl sample was
[7, 9, 13] (606 and 774°ë, respectively), but differ from of high-purity grade and contained 0.2% NaCl,
the values recommended in [14] for LiCl (610°C) and whereas that used in [16] was less pure (of pure grade).
KCl (770°C). We did not verify the homeomorphous
transformation in lithium chloride found in [7, 13]. The
liquidus lines in the figure were constructed by averag- ACKNOWLEDGMENTS
ing equations TL(LiCl) = 607.2 – 3.4198ı – 0.063255ı2 This work was supported by the Siberian Branch of
(with the mean-square deviation from the experimental the Russian Academy of Sciences, Integration Project
points σ = 2.4°ë) and TL(KCl) = 773.97 – 3.4562(100 – ı) – no. 11.
0.023368(100 – ı)2 – 0.00071877(100 – ı)3 (with σ =
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