ISSN 00360244, Russian Journal of Physical Chemistry A, 2012, Vol. 86, No. 4, pp. 590–594. © Pleiades Publishing, Ltd.

, 2012.
Original Russian Text © A.M. Gasanaliev, B.Yu. Gamataeva, Yu.A. Umarova, 2012, published in Zhurnal Fizicheskoi Khimii, 2012, Vol. 86, No. 4, pp. 669–673.

PHYSICAL CHEMISTRY
OF SOLUTIONS

Phase Formation in the LiCl–LiNO3–KCl–Sr(NO3)2 System

A. M. Gasanaliev, B. Yu. Gamataeva, and Yu. A. Umarova
Dagestan State Pedagogical Institute, Makhachkala, Russia
email: umarova.yulduz@yandex.ru
Received February 15, 2011

Abstract—The LiCl–LiNO3–KCl–Sr(NO3)2 fourcomponent system was studied for the first time by a
complex of physicochemical analysis methods, including differential thermal analysis, Xray diffraction,
visualpolythermal, and projection thermographic methods. Eutectic and peritectic invariant point charac
teristics were determined, and the phase diagram of the system was constructed.

Keywords: eutectic, peritectic, multicomponent system.

DOI: 10.1134/S0036024412040097

INTRODUCTION A thermodynamic analysis of systems involving

Complex physicochemical analysis studies of mul
ticomponent systems can be used to create a scientific
basis for chemical technologies of the preparation of
new materials with regulated properties. “Composi
tion–property” phase diagrams are currently the most
informative method for obtaining data on composition
materials [1].
alkali and alkalineearth metal chlorides and nitrates
shows that these composition materials offer promise
for the development of lowmelting salt mixtures that
can be used in medium and lowtemperature heat
accumulators, chemical current sources, as back
ground electrolytes, etc. [2]. In this work, we experi
mentally studied the phase diagram of the LiNO3–
LiCl–KCl–Sr(NO3)2 system.

Table 1. Characteristics of the invariant points of LiNO3–LiCl–KCl–Sr(NO3)2 system bounding elements

Character Composition, mol %

System t, °C Refs.
of points LiCl KCl LiNO3 Sr(NO3)2
LiNO3–LiCl е 252 11.8 – 88.2 – [6]
р 266 18.5 – 81.5 –
LiNO3–KCl e 166 – 40 60 – [8]
р 212 – 21 79 –
KCl–Sr(NO3)2 е 331 – 63 – 37 [6]
р1 360 – 68.4 – 31.6
р2 414 – 73 – 27
LiCl–Sr(NO3)2 е 340 71 – – 29 [8]
LiCl–KCl е 354 58 42 – – [6]
LiNO3–Sr(NO3)2 e 251 – – 98.1 1.9 [7]
LiCl–KCl–Sr(NO3)2 E1 280 64 13 – 23 [8]
P1 290 57.5 28.5 – 14
P2 300 32 39 – 29
LiNO3–LiCl–Sr(NO3)2 E2 234 12.37 – 84.54 3.09 [6]
Р7 242 15 – 83 2
LiNO3–LiCl–KCl Р3 207 1 18.5 80.5 – [6]
LiNO3–KCl–Sr(NO3)2 E3 162 – 38 60 2 [8]
P4 260 – 65 10 25
P5 300 – 54 23 23
P6 210 – 20 79 1

590
 PHASE FORMATION IN THE LiCl–LiNO3–KCl–Sr(NO3)2 SYSTEM 591

Sr(NO3)2
645°

A L
C
K k
M l
N
331°
360° B
14° P5 300 P 260 E P2
4 P3 P1
KCl P2300 E3 162° P6
775° 210
166° 5
234
251°
E2
E1 342° P3 LiNO3
P1 207 252° 254°
290 280° 258°
354° P, 242

LiCl
254°

Fig. 1. Bounding elements of the LiNO3–LiCl–KCl–Sr(NO3)2 fourcomponent system and arrangement of the ABC, MN, KL,
and radial polythermal cuts.

EXPERIMENTAL RESULTS AND DISCUSSION

Studies of the LiNO3–LiCl–KCl–Sr(NO3)2 four
component system were performed by the visualpoly
thermal [3] and differential thermal [4] physicochem
ical analysis methods. Experiment planning and
experimental data interpretation were performed
using the projection thermographic method [3].
Salts were melted in platinum crucibles, the tem
perature was measured by platinum–platinumrhod
ium thermocouples calibrated against the tempera
tures of melting of salts and their eutectic mixtures [4].
The heatingcooling curves were recorded on an EPR
09RD potentiometric unit.
Double and triple systems bounding the system
under consideration were studied in [5–8]. The topol
ogy of the phase diagram of the fourcomponent sys
tem is to a substantial degree determined by the char
acter of interactions in systems with lower dimension
ality. According to the character of component
interactions and topology, binary and ternary systems can
be divided into the following groups (Table 1, Fig. 1):
eutectic systems (LiNO3–Sr(NO3)2, LiCl–Sr(NO3)2,
LiCl–KCl, and LiCl–LiNO3–Sr(NO3)2) and systems
with the formation of incongruently melting com
pounds (LiNO3–LiCl; KCl–Sr(NO3)2, LiNO3–
LiCl–KCl, LiCl–KCl–Sr(NO3)2, and LiNO3–KCl–
Sr(NO3)2).

Table 2. Characteristics of invariant points of the LiCl–KCl–LiNO3–Sr(NO3)2 system

Composition, mol % Character
Notation tm , °C
LiCI KCI LiNO3 Sr(NO3)2 of points

Е 157 3 36 58 3 Eutectic
Р1 193 10 42.5 37.5 10 Peritectic
Р2 204 3 24.5 66.5 6 Peritectic
Р3 218 31 31 27 11 Peritectic

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 86 No. 4 2012

592 GASANALIEV et al.

B
60% LiCl
40% Sr(NO3)2
E1

P1 E P2
M N

P2

P3
K
P1
P3 E2
E P2
A C
40% Sr(NO3)2 P5 E3 P4 40% Sr(NO3)2
60% KCl 60% LiNO3

Fig. 2. ABC polythermal section and arrangement of the MN and KL polythermal sections with radial cuts in it.

t, °C t, °C
l
400 400

l + Sr(NO3)2

300 300
l + Sr(NO3)2 + LiCl

l + Sr(NO3)2 + LiCl + KCl

P1 l + Sr(NO3)2 +
212 LiCl + LiNO3
200 Sr(NO3)2 + LiCl + KCl + S1 200
l + Sr(NO3)2 + l + Sr(NO3)2 +
LiCl + S2
LiCl + S1 P2
174°
E
Sr(NO3)2 + LiCl +
154 LiNO3 + S2
Sr(NO3)2 + LiCl + S1 + S2

100 100
M 0 10 S1 20 S2 30 N
mol %
40% Sr(NO3)2 40% Sr(NO3)2
30% LiCl 30% LiCl
30% KCl 30% LiNO3

Fig. 3. Phase diagram of the MN polythermal section; S1, 3KCl ⋅ 2Sr(NO3)2; S2, 2KCl ⋅ 3Sr(NO3)2.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 86 No. 4 2012

 PHASE FORMATION IN THE LiCl–LiNO3–KCl–Sr(NO3)2 SYSTEM 593

t, °C t, °C
l
300
l + Sr(NO3)2
280
270
260
l + Sr(NO3)2 + KCl 250

l + Sr(NO3)2 +
KCl + LiCl
P3
218

Sr(NO3)2 + KCl +
l + Sr(NO3)2 + KCl + LiNO3
LiCl + S2

174
Sr(NO3)2 + KCl + LiNO3 + S2
K L
0 5 S2 10 15
40% Sr(NO3)2 mol % 40% Sr(NO3)2
45% KCl 45% KCl
15% LiCl 15% LiNO3

Fig. 4. Phase diagram of the KL polythermal section.

To determine the characteristics of invariant points
in this system, we initially selected twodimensional
polythermal section ABC (Fig. 1) in the tetrahedral
diagram, which was situated in the crystallization vol
ume of Sr(NO3)2, by the projection thermography
method. Part of the phase complex and invariant
points present in the system are reflected in the projec
tion onto this section. This section was treated as a
pseudoternary system. We selected two onedimen
sional polythermal sections in it, MN and KL, for
experimental studies. This allowed us to determine the
projections of quaternary invariant points from the A
and B poles (Fig. 2).
The phase diagram of the MN polythermal section
(Fig. 3) constructed using the differential thermal
analysis data allowed us to determine the location of
secondary projection points of eutectic E and peritec
tics P1 and P2 . To determine the coordinates of the pri
mary projections of eutectic E and peritectics P1 and
P2 , we additionally studied radial cuts from pole B
through secondary projection points of eutectic E and
peritectics P1 and P2 (Fig. 1). The coordinates of quater
nary invariant points E and Р1 and Р2 were determined
by studying the Sr(NO3)2–E → Е, Sr(NO3)2–P1 → Р1,
and Sr(NO3)2–P2 → Р2 radial cuts using the intersec
tion of Sr(NO3)2 primary crystallization curves with
quaternary crystallization lines (Table 2, Fig. 1).
We sequentially studied compositions situated on
the KL section by the differential thermal analysis
method. This allowed us to find the P3 point, which
was a secondary peritectic projection (Fig. 4). The coor
dinates of the primary projection of peritectic P3 were
determined by additionally studying a section from pole
A through the secondary projection point of peritectic
P3 . The coordinates of the quaternary invariant point,
Р3, were determined using the Sr(NO3)2–P3 → Р3 radial
cut from the intersection between the Sr(NO3)2 pri
mary crystallization and the quaternary crystallization
curve (Fig. 1).

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 86 No. 4 2012

594 GASANALIEV et al.
To summarize, thermal analysis data on the chlo
ride–nitrate system allowed us to reveal salt composi
tions (Table 2) with melting temperatures of 157–218°С
and high lithium nitrate contents (27–66.7 mol %),
which are the best heat accumulators at temperatures
of from 150 to 500°С. The salt compositions found
offer promise for the development of phasetransition
accumulators capable of reversibly accumulating heat
under iso and nonisothermal conditions [9, 10].
CONCLUSIONS
To summarize, a complex of physicochemical
analysis methods (differential thermal, visual poly
thermal, and Xray) combined with the projection
thermographic method was used to study the LiNO3–
LiCl–KCl–Sr(NO3)2 fourcomponent system char
acterized by developed complex formation and the
presence of four invariant points with melting temper
atures between 157 and 218°С. The melting diagram is
represented by crystallization fields of the initial com
ponents and incongruently melting compounds, S1—
3KCl ⋅ 2Sr(NO3)2 and S2—2KCl ⋅ 3Sr(NO3)2. An
analysis of the topologies of binary through quaternary
systems showed that strontium nitrate occupied the
largest crystallization region in the system. Binary
complex compounds in threecomponent systems and
the fourcomponent system have independent crystal
lization fields bounded by peritectic and transition
points. The fourcomponent system compared with
binary and ternary systems contains the most lowmelt
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
ing region for mediumtemperature (157–500°С)
phase transition thermal accumulators.
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