Journal of Alloys and Compounds 325 (2001) 78–83 L

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Differential scanning calorimetric studies on the phase diagram of the

binary LiCl–CaCl 2 system
K.H. Mahendran, S. Nagaraj, R. Sridharan, T. Gnanasekaran*
Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam — 603 102, Tamilnadu, India
Received 27 February 2001; accepted 26 March 2001

Abstract

The phase diagram of the binary LiCl–CaCl 2 system was investigated by differential scanning calorimetry (DSC). From the
experimental results formation of a compound, LiCaCl 3 at 439648C is discerned. The compound undergoes peritectic decomposition at
4908C. The system shows a eutectic reaction between the compound and solid solution rich in LiCl at 4858C. Also, the system exhibits
significant solid solubility of LiCl(s) in CaCl 2 (s) and vice versa. The complete phase diagram of this system is constructed and reported.
 2001 Elsevier Science B.V. All rights reserved.

Keywords: Phase diagram; Binary system; Differential scanning calorimeter; Endothermic peaks; Eutectic reaction; Peritectic decomposition; Lithium
chloride; Calcium chloride

1. Introduction system, a detailed investigation was undertaken employing

Molten mixtures of alkali and alkaline earth chlorides
when mixed with alkali / alkaline earth hydrides are useful
as hydride ion conducting electrolytes at high temperatures
[1–4]. Phase diagrams of the binary and ternary systems
comprising these materials have not been completely
established. In the case of the LiCl–CaCl 2 system, only a
few studies have been reported. Bukhalova and Arabad-
zhan [5] reported a eutectic reaction at a temperature of
4478C and 64% LiCl as the eutectic composition. A phase
diagram for the LiCl–CaCl 2 system has been given in
‘Phase Diagram for Ceramists’ published in 1964 [6] based
on several Russian investigations. According to this, the
system exhibits eutectic reaction at 4968C and shows solid
solution in the composition ranges of ca. 0.7,XLiCl ,1 and
ca. 0.05.XLiCl .0. This phase diagram was revised in the
supplement issued in 1969 [7]. The revised phase diagram
shows the existence of a compound LiCaCl 3 up to 4418C.
It further shows: decomposition of this compound at
4418C, existence of solid solution regions in the com-
position ranges of ca. 0.83,XLiCl ,1 and ca. 0.16.XLiCl .
0 at T54968C and a eutectic reaction at 4968C with
eutectic composition of |62% LiCl.
In order to resolve the uncertainties in this binary
*Corresponding author. Tel.: 191-4114-40219; fax: 191-4114-40365.
E-mail address: gnani@igcar.ernet.in (T. Gnanasekaran).
the differential scanning calorimetric technique in this
work.
2. Experimental details
Pure CaCl 2 (99.9%; M / s Alfa Products, USA) was
further purified by heating it up to its melting point for 4–5
h in a stream of dry argon gas containing dry HCl. After
the salt was cooled to room temperature it was transferred
into a high purity argon atmosphere glove box that is used
for handling liquid sodium in this laboratory. Analar grade
LiCl (M / s BDH, UK) was also purified in a similar way.
Calculated amounts of purified LiCl and CaCl 2 were
mixed to prepare samples of varying compositions. Weigh-
ing of calculated amounts of LiCl and CaCl 2 , mixing and
grinding of these powders and loading of these samples
(|30 mg) in thin-walled iron / nickel capsules were all
performed in the argon atmosphere glove box. Nickel
capsules (in place of iron) were used to hold pure CaCl 2
and sample having a composition of 5 mol% LiCl, in order
to avoid the thermal effects due to the phase transition
being exhibited by iron containing traces of carbon. The
capsules (of total mass |700 mg) were hermetically sealed
by weld-closing the ends of the capsules by a pulsed
arc-welding unit inside the glove box. The iron capsules
were then brought out and heated up to 8008C and cooled

0925-8388 / 01 / $ – see front matter  2001 Elsevier Science B.V. All rights reserved.
PII: S0925-8388( 01 )01387-1
 K.H. Mahendran et al. / Journal of Alloys and Compounds 325 (2001) 78 – 83 79

in an atmosphere of argon with |2% hydrogen gas mixture

prior to DSC experiments. This was done to ensure
complete equilibration of the sample components and also
to check leak-tightness of the welded capsules. The sample
and empty reference capsules were then introduced into the
furnace of a DSC-111 (M / s. SETARAM, France) equip-
ment. Argon containing |2% hydrogen was used at a flow
rate of 2 l / h during the experiment. Using a programmable
temperature control unit, the sample and the reference
containers could be heated and cooled at any selected
scanning rate. The unit was operated through a personal
computer that is attached to the equipment. The samples
were heated from 25 to 8008C generally at a heating rate of
28C / min. Temperatures corresponding to various thermal
events were obtained from the analysis of the DSC curves
obtained during heating runs because appreciable super-
cooling effects were observed during cooling runs with this
salt system. The DSC runs were repeated for the same
samples at least two times and also for different samples of
the same composition to ensure the reproducibility of the
results. Temperature calibration of the DSC was done
using standard samples of In, Sn and Zn. The uncertainty
in the temperature measurement was 60.58C in the
temperature range of 25–8008C.
The equilibrated samples were loaded in Lindemann Fig. 1. DSC traces obtained for compositions from 5 to 40 mol% LiCl
glass capillaries in the glove box, sealed and the phases and for pure components.
were identified by XRD (D 500 model; M / s Siemens,
Germany). Cu Ka radiation was used for XRD analysis.

2.1. Results

The DSC traces of samples with compositions between

5 and 95 mol% LiCl and those of pure CaCl 2 and LiCl are
shown in Figs. 1–3. The onset temperatures of the endo
peaks were obtained by differentiating the DSC curves and
by noting the temperature at which significant deviation of
the baseline occurs. The results of the DSC experiments of
all samples are summarised in Table 1. The DSC traces,
obtained for pure components, show endothermic peaks
corresponding to the melting of the pure phases. The DSC
traces obtained for all samples of compositions between 10
and 50 mol% LiCl show two predominant endothermic
peaks, one at ca. 4408C and another at ca. 4908C when the
samples are heated. The endothermic peak that begins at
ca. 4908C, tails off and returns to baseline for each
composition of the sample. The DSC trace obtained for 10
mol% LiCl shows a similar pattern but the second endo-
thermic peak begins at 4808C. The DSC traces of samples
with compositions between 50 and 81 mol% LiCl also
show two predominant endothermic peaks, one at ca.
4408C and another at 4858C. The endothermic peak that
begins at 4858C tails off and returns to baseline for each
composition of sample. DSC trace of sample of 58 mol%
LiCl shows a shoulder in addition to the endothermic peak
that begins at 4858C (Fig. 2). The DSC traces obtained for
compositions between 81 and 95 mol% LiCl also show the Fig. 2. DSC traces obtained for compositions from 50 to 76 mol% LiCl.
80 K.H. Mahendran et al. / Journal of Alloys and Compounds 325 (2001) 78 – 83

peak that begins above 4858C tails off subsequently and

the signal returns to the baseline. For compositions be-
tween 62 and 90 mol% LiCl, in addition to these peaks, a
broad and small endothermic peak that begins at |4658C is
observed. The DSC trace obtained for 5 mol% LiCl
showed only a single and broad endothermic peak.

3. Discussion

Results presented in Figs. 1–3 and summarised in Table

1 show that the onset temperature of the first endothermic
peak had been more or less constant (ca. 4408C) for all
samples except for the sample with 5 mol% LiCl where
this thermal event is not observed. The XRD analysis of
the samples (0.10,XLiCl ,0.95) at room temperature, after
equilibrating at a temperature of ca. 4608C followed by
quenching, showed the presence of only two phases,
namely, LiCl(s) and CaCl 2 (s). The possible thermal events
that can give rise to this endothermic peak are:

(i) a phase transition in any one of the pure components

Fig. 3. DSC traces obtained for compositions from 85 to 95 mol% LiCl.
endothermic peak at ca. 4408C. In these samples, another
predominant endothermic peak whose onset temperature is
above 4858C and which increases with increasing CaCl 2
content of the samples, is also observed. The endothermic
before they melt;
(ii) a eutectic reaction between LiCl(s) and CaCl 2 (s) at
this temperature or
(iii) a solid state reaction between LiCl(s) and CaCl 2 to
form a new solid phase at this temperature.
DSC traces obtained for pure LiCl and CaCl 2 (Fig. 1)
show a single endothermic peak at their respective melting

Table 1
Results of the DSC experiments with the LiCl–CaCl 2 system
Serial number Composition of Heating rate Onset temperatures (8C) Liquidus temperature
LiCl–CaCl 2 (mol%) (8C / min) (8C)
First Second
endothermic peak endothermic peak
1 0–100 2 – – 772 a
2 5–95 2 – – 765
3 10–90 2 435 480 735
4 15–85 2 440 490 725
5 20–80 2 439 490 709
6 30–70 2 440 490 670
7 40–60 2 435 490 645
8 50–50 2 435 485 610
9 52–48 2 435 485 580
10 58–42 2 435 485 560
11 62–38 2 435 485 512
12 65–35 2 435 – 485
13 68–32 2 435 485 510
14 72–28 2 441 485 535
15 76–24 2 441 485 545
16 81–19 2 437 490 555
17 85–15 2 442 497 570
18 90–10 2 443 515 585
19 95–05 2 441 545 600
20 100–0 5 – – 605 b
a
Melting point of pure CaCl 2 .
b
Melting point of pure LiCl.
 K.H. Mahendran et al. / Journal of Alloys and Compounds 325 (2001) 78 – 83 81

points. They indicate that pure LiCl and CaCl 2 phases do

not exhibit any phase transition between room temperature
and their respective melting points.
If the endothermic peak at ca. 4408C represents a
eutectic reaction, then the DSC traces must exhibit a broad
tailing of this peak at higher temperatures for all com-
positions except at the eutectic composition since continu-
ous dissolution of one of the solid phases would take place.
The tail would end at corresponding liquidus temperatures.
It can be seen from Figs. 1–3 that this endothermic peak is
observed at all compositions but does not show any tailing.
On the other hand it is followed by another predominant
endothermic peak which has this character. This indicates
that the thermal event at ca. 4408C is isothermal in nature,
but rules out the possibility of a eutectic reaction between
the pure components at this temperature. All these indicate
that the first endothermic peak represents a solid state
reaction between LiCl and CaCl 2 to form a compound ‘X’.
DSC traces of all samples during cooling runs showed that
this endothermic event peak is reversible albeit with Fig. 4. Schematic phase diagram of a binary system exhibiting a
congruently melting compound.
significant supercooling effects. This indicates that during
cooling the decomposition of the compound is kinetically
favourable (a typical cooling curve of 50 mol% LiCl is shown in Fig. 5. Then, two endothermic peaks would be
shown in Fig. 2). This is also indicated by the results of observed in the DSC traces of all samples with com-
the XRD analysis of samples, which had been equilibrated position lying between a and b (a is the composition of the
at ca. 4608C and quenched. The results did not show any maximum solid solubility in component A and b is the
new pattern corresponding to a compound ‘X’. The phases composition of the compound): one at 439648C and the
identified were only the decomposed products, namely, other at the incongruent melting temperature of the com-
LiCl and CaCl 2 phases. From the average of the onset pound with the second endothermic peak tailing off. The
temperatures of this endothermic peak, the temperature temperature corresponding to the tail end would corre-
above which the compound ‘X’ is stable is derived as spond to the liquidus temperature for the chosen com-
439(64)8C. The uncertainty of 648C derived for this position. For samples with composition between b and c (c
thermal event is due to the solid state reactions involved. is the composition of the eutectic), three endothermic
If we assume that the system forms only one compound, events would be expected, the first being the compound
there can be two possible phase diagrams, one when the
compound congruently melts and the other when it melts
incongruently, as shown schematically in Figs. 4 and 5,
respectively.
In the case of congruent melting of the compound, the
phase diagram exhibits two eutectic reactions on both sides
of the composition corresponding to the compound (Fig.
4). DSC trace of samples with composition corresponding
to these eutectics and that of the compound at ‘b’ would
show two endothermic peaks, one at 439648C and the
other at a higher temperature corresponding to the eutectic
or congruent melting temperatures. The second endother-
mic peak also would not show any tailing, as this event
would also be an isothermal event. Samples with any other
composition would show the tailing of the second peak and
the temperature corresponding to the tail-end (i.e. where
the trace returns to the baseline) would yield the liquidus
temperature. At the extremes of the compositions, i.e.
closer to the pure components, characteristics owing to
formation of solid solution could be observed.
In the case where the compound melts incongruently, Fig. 5. Schematic phase diagram of a binary system exhibiting an
the phase diagram can be schematically represented as incongruently melting compound.
82 K.H. Mahendran et al. / Journal of Alloys and Compounds 325 (2001) 78 – 83
formation at 4398C. The second event would correspond to
the eutectic halt while the third would represent the
incongruent melting and would tail off at the liquidus
temperature. At the eutectic composition, the first endo-
thermic event would be at 4398C and the second at the
eutectic halt without any tailing of the latter. For com-
positions between the eutectic and that corresponding to
the maximum solubility (in component B), two endo-
thermic events would be observed, one at 4398C and
another at the eutectic temperature, with the tailing of latter
up to the liquidus temperature.
In the event of the system forming additional com-
pounds above 4398C, additional isothermal halts for their
formation and for their congruent / incongruent melting
would also be observed.
DSC traces obtained (Fig. 2) from the present work for
compositions from 50 to 81 mol% LiCl, except for 65
mol% LiCl, show that the second predominant endo-
thermic peak tails off and returns to baseline. The tempera-
tures corresponding to the tail ends give the liquidus
temperatures of the respective compositions. For the
sample with 65 mol% LiCl, the second endothermic peak
does not show any tailing and hence corresponds to an
isothermal event. Table 1 shows that the liquidus tempera-
tures decrease monotonically with composition up to 65
mol% LiCl and then rise with increasing LiCl composition
until the melting point of pure LiCl is reached. The DSC
traces shown in Fig. 1 for compositions between 0 and 50
mol% LiCl and the data summarised in Table 1 indicate
that the liquidus temperatures of samples decrease continu-
ously with increasing content of LiCl. It is evident from all
these observations that the minimum of the liquidus
temperature corresponds to the eutectic temperature and is
4858C. The eutectic composition is close to 65 mol% LiCl
which is in agreement with that reported in Ref. [7]. The
eutectic temperature obtained in this work is 4858C
whereas it was reported as 4968C in Refs. [6,7].
The monotonic decrease in liquidus temperatures from
100% CaCl 2 to 65 mol% LiCl and subsequent increase up
to 100% LiCl resulting in a single minimum of liquidus
temperatures, suggest that the compound ‘X’ that is formed
at 4398C does not undergo congruent melting but under-
goes peritectic decomposition as schematically depicted in
Fig. 5. Further evidence for the peritectic decomposition
comes from the onset temperatures of the second endo-
thermic peak in samples with composition between 10 and
50 mol% LiCl. The onset temperature is constant at 4908C
and is not at 4858C in this composition range (Table 1).
These observations put together suggest that the high
temperature compound between CaCl 2 and LiCl is formed
at 50 mol% LiCl, and undergoes peritectic decomposition
at 4908C. The compound LiCaCl 3 is reported in Ref. [7] to
exist below 4418C whereas the results of this work show
that the compound forms at 439648C and peritectically
decomposes at 4908C. It can be noted from the DSC traces
of samples with compositions between 50 and 65 mol%
LiCl that the endothermic peak for peritectic decomposi-
tion at (4908C) overlaps with the endothermic peak for
eutectic melting (4858C). This can be clearly discerned
from the DSC trace shown by the sample of 58% LiCl
composition (Fig. 2) where a shoulder appears in the
endothermic peak that begins at 4858C. The endothermic
peaks for eutectic and peritectic reactions could not be
resolved as the events occur within a narrow temperature
span of 58C.
The DSC traces obtained in the terminal region (for
compositions between 80 and 100 mol% LiCl, see Fig. 3)
did not show the eutectic reaction at 4858C. For these
compositions, a broad endothermic peak starts at tempera-
tures above 4858C and tails off up to the liquidus tempera-
tures corresponding to each composition. The characteris-
tic feature of these endothermic peaks is that they begin at
increasingly higher temperatures with increasing concen-
tration of LiCl. This observation and the absence of a
eutectic reaction indicate that solid solution of CaCl 2 in
LiCl phase occurs in this terminal region. The tempera-
tures corresponding to the beginning of the endo peaks
beyond 4858C, represent solidus temperatures of the LiCl-
rich solid solution in this composition range. Considering
the fact that the system exhibits a solid-solution region at
high temperatures between 80 mol% LiCl and pure LiCl,
the small and broad endothermic peak, which begins at
|4658C for compositions between 62 and 90 mol% LiCl,
could represent rapid dissolution of one solid phase into
the other. This is attributed to the probable inflection of the
boundary curve at the LiCl-rich side of solid-solution. This
small endothermic peak tails off at 4818C and at 4758C for
85 and 90 mol% LiCl compositions, respectively.
The DSC trace obtained for 5 mol% LiCl did not show
any clear evidence of eutectic, peritectic or solid state
reaction. It shows a single broad endothermic peak that
emerges gradually from baseline near 5508C and tails off
at 7658C which corresponds to its liquidus temperature.
The absence of thermal events for the solid state reaction
between LiCl and CaCl 2 at ca. 4398C and for the peritectic
reaction at 4908C, respectively, implies that this com-
position corresponds to a region of solid solution of LiCl
in CaCl 2 phase. For the sample with 10 mol% LiCl, the
second endothermic event starts at 4808C and not at 4908C
and this was discerned by the method adopted to analyse
the DSC traces, viz differentiating them and locating the
temperature at which significant deviation from the
baseline occurs. Hence, this temperature does not corre-
spond to peritectic decomposition of the compound.
Beyond this temperature the liquidus point only could be
clearly discerned from DSC trace. Hence the thermal event
recorded at 4808C corresponds to dissolution of a signifi-
cant amount of LiCaCl 3 into CaCl 2 phase. For samples of
5 and 10 mol% LiCl the solidus temperatures could not be
discerned from the DSC traces presumably due to less
 K.H. Mahendran et al. / Journal of Alloys and Compounds 325 (2001) 78 – 83 83

tions of LiCl and CaCl 2 . LiCl and CaCl 2 form a com-

pound, LiCaCl 3 at 439(64)8C which undergoes peritectic
decomposition at 4908C. The system shows a eutectic
reaction between the compound and solid solution rich in
LiCl at 4858C. The eutectic composition is very close to 65
mol% LiCl. The system exhibits solid solutions at both the
terminal compositions. The composition of the solid
solution is ca. 10 mol% LiCl on the CaCl 2 -rich side of the
phase diagram at 4908C. On the LiCl-rich side, the
composition of the solid solution is ca. 20 mol% CaCl 2 at
4858C.

References

[1] R.B. Holden, N. Fuhrman, Proc. International Conference on

Fig. 6. Phase diagram of the binary LiCl–CaCl 2 system established from
this work.
intensive heat effects. Based on the above discussions, the
phase diagram of LiCl–CaCl 2 is constructed and is shown
in Fig. 6.
4. Conclusion
The phase diagram for the LiCl–CaCl 2 system is
constructed based on DSC analysis of various composi-
Sodium Technology and Large Fast Reactor Design, Argonne, IL,
November 7–9, 1968, U.S. Atomic Energy Commission Report,
ANL-7520-(1), p. 262.
[2] C.A. Smith, Berkeley Nuclear Laboratories, Central Electricity
Generating Board, UK, Report R / D/ BN-2331, 1972.
[3] T. Gnanasekaran, K.H. Mahendran, R. Sridharan, V. Ganesan, G.
Periaswami, C.K. Mathews, Nucl. Technol. 90 (1990) 408.
[4] R. Sridharan, K.H. Mahendran, T. Gnanasekaran, G. Periaswami,
U.V. Varadaraju, C.K. Mathews, J. Nucl. Mater. 223 (1995) 72.
[5] G.A. Bukhalova, A.S. Arabadzhan, Zh. Neorg. Khim. 7 (1962)
2230.
[6] Fig. 1291 E.M. Levin, C.R. Robbins, H.F. McMurdie (Eds.), Phase
Diagram for Ceramists — 1964, 3rd Edition, The American Ceramic
Society, OH, 1974, p. 382.
[7] Fig. 3085 E.M. Levin, C.R. Robbins, H.F. McMurdie (Eds.), Phase
Diagram for Ceramists — 1969 Supplement, The American Ceramic
Society, OH, 1969, p. 299.