2002 The Phase Diagram of LiNO3-KNO3

Thermochimica Acta 385 (2002) 81–84
The phase diagram of LiNO3–KNO3

Xuejun Zhang, Kangcheng Xu*, Yici Gao
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
Received 25 April 2001; received in revised form 18 July 2001; accepted 1 August 2001
Abstract
The binary phase diagram of LiNO3–KNO3 are studied by means of differential scanning calorimeter (DSC). The
convincing evidence for the identification of new phase has been presented. The phase diagram indicates an intermediate
compound KLi(NO3)2, which melts congruently at 428 K. The coordinates of two eutectic points are 420 K, 47 mol% KNO3
and 410 K, 54 mol% KNO3. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Phase diagram; LiNO3–KNO3 system; Congruently melting compound
1. Introduction 2. Experimental
The system of LiNO3–KNO3 is usually regarded as The thermal analyses were carried out on a Perkin-
a simple eutectic one [1,2], although some researchers Elmer DSC-7 differential scanning calorimeter. The
[3] have noted that in addition to the eutectic point calibration of the instrument was made by high purity
at xðLiþ Þ ¼ 0:41, there was another discontinuity at indium and zinc as standard samples.
xðLiþ Þ ¼ 0:45 which was tentatively attributed to an Reagent grade potassium nitrate and lithium nitrate
intermediate incongruently melting compound. This were recrystallized from redistilled water and dried in
observation seems to have been neglected by some the oven at approximately 378 K for 3 days. The dried
investigators using the liquid mixtures of LiNO3– chemicals were weighed at definite ratios, mixed well
KNO3 [2,4]. No further thermal measurements have in a mortar and transferred to quartz crucibles. The
been attempted to explore the origin of the disconti- mixtures were dried for 3 days, first at 333 K, then
nuity. Raman spectroscopic studies [5,6] indicated that 378 K, and finally at 403 K. Then the temperature was
a congruently melting compound KLi(NO3)2 was gradually raised until the mixtures were completely
formed. The new compound can be prepared from melted. The samples were kept in molten state for at
quenched samples. least 12 h to achieve well-mixed and homogenous
In this work, we determined the phase diagram of compositions for the mixtures. Then the quenched
LiNO3–KNO3 by differential scanning calorimetry samples were ground into a fine powder and stored
and calculated their phase diagram. over desiccant.
At least three successive runs were carried out for
each sample. Generally, the results of the third run were
in agreement with those of the second run (indicating
*
Corresponding author. Fax: þ86-931-8912586. equilibrium conditions) and only third data are reported
E-mail address: zhaxj@yahoo.com (K. Xu). here. The heating and cooling rates are 10 K min1, and
0040-6031/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 3 1 ( 0 1 ) 0 0 7 0 4 - 3
82 X. Zhang et al. / Thermochimica Acta 385 (2002) 81–84
the dry N2 sweep rate through the DSC assembly was 4. Results and discussion
20 cm3 min1, the samples (5–20 mg) were placed in
open aluminum pans. Fig. 1 shows the DSC profiles for the salt mixtures
of the LiNO3–KNO3 system. The DSC profile of
1:1 mixture (mole fraction of KNO3, x ¼ 0:5) shows
3. Thermodynamic relationships the typical of the congruently melting compound
KLi(NO3)2. To determine the eutectic composition,
For equilibrium between a solid and a liquid phase the sharpness of the DSC peaks (expressed by the ratio
in a binary system with components A and B, the of peak height to half the width) were compared from
Gibbs energy of fusion of A may be expressed as sample to sample in the composition range x ¼ 0:4–
0.6 at 1% intervals. The sharpest peaks were observed
xA ð‘Þ
Dfus GA ¼ RT ln þ GEA ð‘Þ GEA ðsÞ (1) for the sample of x ¼ 0:47 and x ¼ 0:54. The eutectic
xA ðsÞ temperatures were determined from the heating and
where xA(‘) and xA(s) are the mole fractions of A on cooling profiles of these compositions.
the liquidus and solidus at temperature T respectively, The data for solidus and for liquidus are listed in
and R is the gas constant. GEA ð‘Þ and GEA ðsÞ are the Table 1 and graphically displayed in Fig. 2. The phase
partial excess Gibbs energies of A in the liquid and diagram clearly indicates the occurrence of intermedi-
solid. In this system the excess entropy SE(‘) and SE(s) ate compound KLi(NO3)2, which melts congruently at
were set to equal zero. So GE ¼ H E . The partial 428 K. The coordinates of two eutectic points are
properties can be obtained from the integral property 420 K, 47 mol% KNO3 and 410 K, 54 mol% KNO3.
from the following equation: None of the investigations has reported the solid
solubility, although some solubility of LiNO3 and
dH E
GEi ¼ HiE ¼ H E þ ð1 xi Þ (2) KNO3 may be expected. Solid solutions have not been
dxi examined in this work too. Earlier, the calculations
where i ¼ A or B. about the system were performed by one simple
HE may be expanded as ploynomials in the mole eutectic system [2,7]. Those calculation values were
fractions as follows [10]: below the experimental values. In the present work,
calculations were performed under the assumption of
H E ¼ xA xB ðh0 þ h1 xB þ þ hi xB Þ (3)
zero solid solubility and the intermediate compound
where the hi is empirical coefficients. KLi(NO3)2 was used.
Fig. 1. DSC profiles of the mixture of KNO3 and LiNO3.

X. Zhang et al. / Thermochimica Acta 385 (2002) 81–84 83
Table 1 The system was dealt with two simple eutectic

DSC data of the system LiNO3–KNO3
portions. For each portion, under the assumption that
Mole fraction Eutectic temperature, Liquidus tempeature, GE(‘) is given by Eq. (4), a phase diagram was
KNO3 T (K) TL (K) calculated. At the eutectic temperatures of 410 and
1 2 420 K, the calculated liquidus compositions were
xB ¼ 0:47 and xB ¼ 0:54, in very good agreement
0.0 527.5
with the experiment eutectic compositions. The cal-
0.1 514.3
0.2 497.7 culated Gibbs energy of fusion (in J mol1) of the
0.3 420 477.9 compound KLi(NO3)2 is
0.4 420 450.6
0.45 420 431.5 Dfus G ¼ 19410 23:120T (5)
0.47 420 420.1
0.49 420 425.3
The calculated liquidus is displayed by a solid line in
0.50 428.0 Fig. 2. Probable maximum inaccuracy in calculated
0.52 410 418.6 liquidus is 5 K. The broken line indicates that the
0.54 410 410.0 compound KLi(NO3)2 is unstable. The congruently
0.56 410 419.1 melting compound KLi(NO3)2 could only exist in a
0.58 410 428.6
0.60 410 437.6
narrow composition range at the equimolar point and
0.7 410 481.2 in a short temperature range just below the solidus.
0.8 527.4 Standing at room temperature, KLi(NO3)2 decom-
0.9 570.1 posed gradually into LiNO3 and KNO3.
1.0 608.0 For the series of lithium nitrate with the other alkali
metal nitrates, the size difference between the cations
The excess enthalpy (in J mol1) was measured at in LiNO3–RbNO3 is sufficiently large to permit for-
618 K in solid–liquid mixing experiments by Kleppa mation of the congruently melting compound
and Hersh, and the results are used here [8]: RbLi(NO3)2 [1,9]. There seems to be little debate
about the phase diagram LiNO3–RbNO3. For
H E ð‘Þ ¼ xA xB ð7352:6 363:7xA 1935:3xA xB Þ
LiNO3–CsNO3 the early investigations [1] indicated
(4) eutectic or solid solution formation but these sugges-
Fig. 2. The phase diagram for the LiNO3–KNO3 system.

84 X. Zhang et al. / Thermochimica Acta 385 (2002) 81–84
tions were questioned [9] since the congruently melt- 5. Conclusions

ing compound had already been observed for LiNO3–
RbNO3. Bol’shakov et al. [9] reinvestigated the The convincing evidence for the identification of
binary nitrates and a congruently melting compound new phase has been presented in our work. This
CsLi(NO3)2 was detected at 467 K. The existence of studies suggested that a congruently melting com-
the compound was confirmed by other authors [10,11]. pound KLi(NO3)2 was formed in the system of
LiNO3–KNO3 is usually regarded as a eutectic system, LiNO3–KNO3 formerly regarded as a simple eutectic
although a discontinuity at xðLiþ Þ ¼ 0:45 in the liqui- system, and the KLi(NO3)2 forms eutectic mixtures
dus was observed in the phase diagram by some early with the end members. This result is identical with
researchers [3,12], No further studies have been thermodynamic calculation.
attempted to explore the origin of the discontinuity.
Complete disappearance of the Raman features of
the two initial components implies absence of the Acknowledgements
structure of either LiNO3 or KNO3. Although no
crystallographic data are available, the new features The authors would like to acknowledge the financial
in Raman spectrum of the quenched sample indicated support by the Natural Science Foundation of Gansu
that an entirely new structure, being very similar to Province.
those congruently melting compound RbLi(NO3)2 or
CsLi(NO3)2, had been created in the equimolar
LiNO3–KNO3 solid [5,6]. The new structure corre- References
sponds to the compound KLi(NO3)2 which has been
overlooked previously by thermal analysis. [1] N.K. Voskresenskaya (Ed.), Handbook of Solid–Liquid
In binary systems with a common anion, and invol- Equilibria in Systems of Anhydrous Inorganic Salts, Vol. I,
ving lithium salts, the occurrence of intermediate com- Kete Press, Jerusalem, 1970.
pounds is not surprising, in view of the small cation Liþ. [2] M.J. Maeso, J. largo, Thermochim. Acta 223 (1993) 145.
[3] C. Vallet, J. Chem. Thermodyn. 4 (1972) 105.
The second cation, a larger one, can thus easily coor- [4] M.H. Brooker, A.N. Fletcher, J. Electroanal. Chem. 221
dinate the anions around it. This may lead to formation (1987) 115.
of a new compound. The function of larger Kþ, Rbþ or [5] K. Xu, J. Phys. Chem. Solid 60 (1999) 5.
Csþ appears to make it possible for the already existing [6] K. Xu, Y. Chen, J. Phys. Chem. Solid 60 (1999) 317.
coordination between lithium and nitrate ions to be [7] Y. Dessureault, J. Sangster, A.D. Pelton, J. Chim. Phys. 87
(1990) 407.
retained in the crystal when the temperature decreased [8] O.J. Kleppa, L.S. Hersh, J. Chem. Phys. 34 (1961) 351.
and the congruently melting compound formed. As was [9] K.A. Bol’shakov, B.I. Pokrovskii, V.E. Plyushchev, Russ.
noted previously, the compounds KLi(NO3)2 had broad J. Inorg. Chem. 6 (1961) 1083.
bands over the whole spectrum and a strong Rayleigh [10] Y.G. Litvinov, I.I. Il’yasov, V.I. Savva, Russ. J. Inorg. Chem.
wing. This is typical for polymeric structures. It seems 20 (1975) 1418.
[11] I.I. Il’yasov, T.I. Dunaeva, Y.G. Litvinov, V.V. Vochanskaya,
likely that the nitrate ions remained bridging the lithium Russ. J. Inorg. Chem. 21 (1976) 1266.
ions to form polymeric complexes in the congruently [12] C. Sinistri, P. Franzosini, Ric. Sci. Parte 2, Sez. A 4 (1963)
melting compounds. 419.

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Thermochimica Acta 385 (2002) 81–84

The phase diagram of LiNO3–KNO3

Keywords: Phase diagram; LiNO3–KNO3 system; Congruently melting compound

Fig. 1. DSC profiles of the mixture of KNO3 and LiNO3.

Table 1 The system was dealt with two simple eutectic

Fig. 2. The phase diagram for the LiNO3–KNO3 system.

tions were questioned [9] since the congruently melt- 5. Conclusions

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