Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 109–114

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Optimization and calculation of the NdCl3–MCl (M = Li, Na, K, Rb, Cs)

phase diagrams
Yimin Sun∗, Xinyu Ye, Yu Wang, Junjun Tan
Institute of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, PR China

Received 23 March 2004; received in revised form 9 July 2004; accepted 27 July 2004
Available online 21 August 2004

Abstract

The binary phase diagrams of the NdCl3 –MCl (M = Li, Na, K, Rb, Cs) systems were studied using the CALPHAD technique. For
describing the Gibbs energies of the liquid phase in these systems, the new modified quasi-chemical model in the pair-approximation
for short-range ordering was used. Based on measured phase equilibrium data and experimental thermochemical properties, a set of
thermodynamic functions has been optimized using an interactive computer-assisted analysis, which was applied to calculate the self-
consistent thermodynamic phase diagrams.
© 2004 Elsevier Ltd. All rights reserved.
Keywords: Optimization and calculation; Rare earth chloride; Alkali metal chlorides; Phase diagrams; Mixing enthalpy

1. Introduction 2. Experimental information

2.1. Data of phase diagrams

Molten salts are being considered for use as fluid targets
in the nuclear incineration of transuranium elements with A few phase diagrams of these systems have been pub-
proton accelerators [1]. The molten salts are also used as lished [1,7–21]. However, the results and their interpre-
the media in high temperature chemical reprocessing of tation were contradictory to some extent. The earlier re-
spent nuclear fuel of fast reactors. The phase diagrams of sults by Morozov et al. on the systems of NdCl3 –NaCl [7],
rare earth metal halides in combination with alkali metal NdCl3 –KCl [8], NdCl3 –RbCl [9], and NdCl3 –CsCl [10]
halide systems are of prime importance for considering their are probably not correct because of their visual-polythermal
application. method, the melting point (m.p. 1049 K) for the NdCl3 they
To continue our previous work [2–6], the thermodynamic measured is higher than that by others. The NdCl3 –MCl sys-
optimizations of the NdCl3 –MCl (M = Li, Na, Rb, Cs) tems, except for NdCl3 –LiCl, were remeasured by Seifert
systems are reported in this paper. We optimized the phase et al. several years later [11,12]. Also Foerthmann et al. [13,
diagrams thermodynamically from available data including 14] and Zheng et al. [15,16] remeasured the NdCl3 –NaCl
those of phase equilibria measured by DTA (differential and NdCl3 –KCl systems, respectively. Their papers de-
thermal analysis), XRD (X-ray diffraction) and experimental scribed that there was no intermediate compound in the
thermochemical properties. NdCl3 –NaCl system but a few compounds (K2 NdCl5 and
K3 NdCl6 in [14], K3 NdCl6 in [16]) in the NdCl3 –KCl
system. Furthermore, the phase diagram of NdCl3 –NaCl
was also determined by Igarashi et al. [17] and Sharma
and Rogers [18] and Sato and Ogawa [1]; the NdCl3 –LiCl
∗ Corresponding author. system was reexamined by Zhang et al. [19] and Kim
E-mail address: [email protected] (Y. Sun). et al. [20]; A high-temperature study of phase equilibria

0364-5916/$ - see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.calphad.2004.07.004
110 Y. Sun et al. / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 109–114

Fig. 1. Enthalpy of mixing in the NdCl3 –MCl melts. Fig. 2. Interaction parameters versus mole fraction of NdCl3 .

in the NdCl3 –CsCl system was undertaken by Lisek and

coworkers [21], which basically confirmed the result of
Seifert et al. [11,12]. By comparing the results above, three
of these investigations [1,11,19] (shown in Figs. 3–7, in
which open circles denote the experimental data) were cho-
sen in the course of our calculations. The purity of the
reagents they used, especially NdCl3 , is higher and the ther-
mal analysis of phase diagrams seems more reasonable than
others as well, so their results should be more trustwor-
thy. The phase diagram of the NdCl3 –LiCl system came
from Zhang et al. [19] with a eutectic point at 28.5(wt%)
LiCl and 725 K. A metastable compound, LiNd2 Cl7 , was
shown to form in the solid state with temperature of de-
composition at 716 K. Seifert et al. [11] studied all the
other systems. The following double chlorides were found:
Na3 Nd5 Cl18 ; K3 NdCl6 , K2 NdCl5 , KNd2 Cl7 ; Rb3 NdCL6 ,
Rb2 NdCl5 , RbNd2 Cl7 ; Cs3 NdCl6 , Cs2 NdCl5 , CsNd2 Cl7 . Fig. 3. Phase diagram of NdCl3 –LiCl.
The crystal structures of the compounds were determined by
X-ray diffraction on powders. But for the NdCl3 –NaCl sys- The free energies of fusion are given by:
tem, we choose the result from Sato and Ogawa [1] instead
of that by the Seifert group [11] because the latter results
G 0fus = A + BT + C T 2 + DT ln T + E/T J mol−1 .
were slightly modified by the former. The peritectic reaction
was found to occur at 813 ± 7 K. The peritectic compound
was confirmed to be Na3 Nd5 Cl18 by means of X-ray diffrac- Table 1
tion analysis. The homogeneity range of Na3 Nd5 Cl18 could Thermodynamic properties of pure compounds
not be defined accurately, but appeared to be between 59 and Compound Tfus (K) A × 10−3 B C × 103 D E × 10−5
70 mol% of NdCl3 at temperatures between 573 and 813 K.
LiCl 883 4.416 197.32 16.435 −31.966 0
All the above are almost the same in both articles except for NaCl 1074 7.735 202.09 11.924 −31.824 0
the eutectic temperature. Ogawa’s one is at 713 ± 4 K, 10 K KCl 1044 4.755 215.398 12.734 −33.581 182.42
higher than that reported by Seifert et al. [11], but in agree- RbCl 993 7.758 96.731 5.209 −15.899 0
ment with that reported by Sharma and Rogers [18]. CsCl 918 1.755 116.392 2.4686 −17.673 0
NdCl3 1032 10.469 433.05 30.55 −68.41 0

2.2. Thermodynamic properties of pure components

2.3. Integral property
All thermodynamic data of pure components come from
the FACTBASE [22] and USERBASE (Table 1), in which The results of calorimetric investigations of mixing
we stored the latest published thermodynamic data. enthalpies of neodymium(III) chloride with alkali chloride
 Y. Sun et al. / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 109–114 111

Fig. 6. Phase diagram of NdCl3 –RbCl.

Fig. 4. Phase diagram of NdCl3 –NaCl.

Fig. 5. Phase diagram of NdCl3 –KCl. Fig. 7. Phase diagram of NdCl3 –CsCl.

were carried out by Gaune-Escard et al. [23] by using a

break-off ampoule technique, and the group also used the A A, B B and AB are considered.
Hoch–Arpshofen solution model to analyze the data [24]. (A–A)pair + (B–B)pair = 2(A–B)pair . (1)
The NdCl3 –LiCl system is the only one for which the
mixing enthalpy is not available. The experimental data Let n A and n B be the number of moles of A and B and
are shown as points in Fig. 1 (Hmix) and Fig. 2 (λM = n i j be the number of moles of (i – j ) pairs. Let Z A and Z B

H /(X MCl X NdCl3 )). be the coordination numbers of A and B. Then
Z A n A = 2n A A + n AB (2)
3. Optimization and calculation Z B n B = 2n A A + n AB . (3)
And let Z i j be the coordination number of i in the i – j pair
3.1. Thermodynamic model


1 1 2n A A n AB
= + (4)
In order to optimize the phase diagram with short- ZA 2n A A + n AB Z A A Z AB
range ordering, a modification of the quasi-chemical

1 1 2n B B n AB
theory of Guggenheim [25,26] was made by Pelton and = + (5)
ZB 2n A A + n AB Z B B ZBA
Blander [27–30]. Instead of the real components of the
system, first-nearest-neighbor pairs are used in the new where Z A A and Z AB are the values of Z A when all nearest
approach. For instance, if A and B are the real components neighbors of an A are As, and when all nearest neighbors of
in an A–B binary system, three first-nearest-neighbor pairs an A are Bs, and where Z B B and Z B A are defined similarly.
112 Y. Sun et al. / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 109–114

Table 2
Calculated coefficients for the NdCl3 –MCl systems

System C1 C1 C1 C1 C2 C2
( j = 0) ( j = 1) ( j = 2) ( j = 4) ( j = 0) ( j = 1)
X AA XBB X AA XBB X AA XBB X AA XBB

LiCl −6213.9 1282.7 3220.3 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
NaCl −3803.1 −2155.1 −6234.6 0.0000 −259.5 0.0000 0.0000 −3.556 3.558 0.768
KCl −11489.5 6181.1 − 6884.4 −11327.5 −7820.3 8569.9 0.0000 0.0000 0.0000 0.0000
RbCl −11050.9 −19048.5 −18945.5 26904.4 0.0000 −12600.4 0.0000 5.415 −1.911 0.0000
CsCl −17410.2 3197.7 −2979.8 −383.5 −14308.3 −1111.3 0.0000 0.0000 0.0000 0.0000

Also the pair fraction X i j is defined as For Eqs. (14) and (15), i + j ≥ 1, in practice we will
always have either i = 0 or j = 0.
X i j = n i j /(n A A + n B B + n AB ). (6)
Overall mole fractions: 3.2. Optimization
X A = n A /(n A + n B ) = 1 − X B . (7)
The experimental data of the interaction parameter
And “coordination–equivalent” fractions. λM =
H /(XMClXNdCl3 ) versus the mole fraction of
Y A = Z A n A /(Z A X A + Z B n B ) NdCl3 (Fig. 2) show that for the NdCl3 –MCl mixtures,
the broad minimum values in λM are found near
= Z A X A /(Z A X A + Z B X B ) XNdCl3 = 0.2 to 0.3. Therefore, the liquid phase of
= 1 − YB . (8) the NdCl3 –MCl systems are considered as short-range
Substitution of Eqs. (2) and (3) into (6) and (8) gives ordering. So the new modified quasi-chemical model for
short-range ordering is chosen to describe the Gibbs
Y A = X A A + X AB /2 (9) energies of the liquid. To calculate the phase diagrams,
Y B = X B B + X AB /2. (10) the coordination numbers Z i j should be determined first.
For the binary rare earth halide systems, supposing the
The Gibbs energy of the solution is given by
RE, M as A, B, Z A A and Z B B were both set equal
G = (n A g 0A + n B g 0B ) − T
S config + n AB /2
g AB (11) to 6 experimentally [30,31]. In the RECl3 –MCl system,
there is a tendency to form the compound RECl3 ·3MCl,
where g 0A and g 0B are the molar Gibbs energies of the pure
i.e., K3 NdCl6 Rb3 NdCL6 , Cs3 NdCl6 , so in the pair A–B,
components, and
S config is the configurationally entropy of Z AB :Z B A is equal to 3:1 Therefore, the coordination
mixing given by randomly distributing the (A–A), (B–B), numbers are accepted as Z MM = 6, Z NdNd = 6, Z MNd = 2
and (A–B) pairs. and Z NdM = 6.

S config = −R(n A ln X A + n B ln X B )
 
X AA XBB X AB Table 3
− R n A A ln 2 + n B B ln 2 + n AB ln . Thermodynamic properties of intermediate compounds
YA YB 2Y A Y B
Intermediate 0 (K)
Tfus
G 0f ( A B ) = a + bT
(12) m n
compound (∗ Decomposition (J mol−1 )
Then Gibbs energy of the A–B system is given by temperature) a × 10−3 b
Eq. (13): (Cal.) (Cal.)

G = (n A g 0A + n B g 0B ) + RT (n A ln X A + n B ln X B ) Na3 Nd5 Cl18 813∗ 29.5000 73.5675

  K3 NdCl6 972 19.0000 88.0169
X AA XBB X AB K2 NdCl5 883∗ −20.0000 15.3143
+ RT n A A ln 2 + n B B ln 2 + n AB ln
YA YB 2Y A Y B KNd2 Cl7 783∗ 4.20000 38.1255
Rb3 NdCl6 1060 −15.6 54.6504
n AB 828∗ −40.7000
+
g AB . (13) Rb2 NdCl5 5.5979
2 RbNd2 Cl7 864∗ −8.6000 30.3376
The molar energy of A–B pairs,
g AB , is a function Cs3 NdCl6 1108 −40.9000 65.7640
CsNd2 Cl7 906∗ −24.800 33.1643
of the mole fractions of i – j pairs and can be expressed as
follows.
  j j

g AB =
g 0AB + g iAB X iA A + g AB X B B (14) All collected data including phase diagram data and
thermochemical enthalpies of mixing are used together to
or
 ij j
optimize the thermodynamic properties and phase diagrams

g AB =
g 0AB + g AB X iA A X B B . (15) by using a simple computer program.
 Y. Sun et al. / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 109–114 113

Table 4
Invariant temperatures and compositions for the NdCl3 –MCl binary systems

System Reaction Calculated values Experimental values Type

T (K) Comp. (mol% NdCl3 ) T (K) Comp. (mol% NdCl3 )

NdCl3 –LiCl L ↔LiCl + NdCl3 724.97 0.297 725 0.298 Eutectic

NdCl3 –NaCl L ↔NaCl + Na3 Nd5 Cl18 713.13 0.35 713 0.35 Eutectic
L + NdCl3 ↔Na3 Nd5 Cl18 811.95 0.50 813 0.48 Peritectic
NdCl3 –KCl L ↔KCl + K3 NdCl6 894.07 0.166 899 0.16 Eutectic
L ↔K3 NdCl6 964.65 (0.25) 972 (0.25) Congruent point
L + K3 NdCl6 ↔K2 NdCl5 882.81 0.352 883 0.335 Peritectic
L ↔K2 NdCl5 + KNd2 Cl7 760.60 0.543 766 0.54 Eutectic
L + NdCl3 ↔KNd2 Cl7 784.91 0.593 783 0.60 Peritectic
K3 NdCl6 ↔KCl + K2 NdCl5 713.19 719 Decomposition
KNd2 Cl7 ↔K2 NdCl5 + NdCl3 740.18 742 Decomposition
NdCl3 –RbCl L ↔RbCl + Rb3 NdCl6 905.83 0.120 905 0.12 Eutectic
L ↔Rb3 NdCl6 1057.13 (0.25) 1060 (0.25) Congruent point
L + Rb3 NdCl6 ↔Rb2 NdCl5 831.45 0.421 828 0.42 Peritectic
L ↔Rb2 NdCl5 + RbNd2 Cl7 783.01 0.490 784 0.495 Eutectic
L + NdCl3 ↔RbNd2 Cl7 863.96 0.664 864 0.66 Peritectic
Rb3 NdCl6 ↔RbCl + Rb2 NdCl5 667.15 667 Decomposition
RbNd2 Cl7 ↔Rb2 NdCl5 + NdCl3 631.18 630 Decomposition
NdCl3 –CsCl L ↔CsCl + Cs3 NdCl6 863.06 0.09 863 0.09 Eutectic
L ↔Cs3 NdCl6 1114.34 (0.25) 1108 (0.25) Congruent point
L ↔Cs3 NdCl6 + CsNd2 Cl7 784.40 0.45 785 0.45 Eutectic
L ↔CsNd2 Cl7 904.69 (0.666) 906 (0.666) Congruent point
L ↔CsNd2 Cl7 + NdCl3 894.71 0.728 891 0.725 Eutectic
Cs3 NdCl6 ↔CsCl + CsNd2 Cl7 678.45 678 Decomposition

3.2.1. Heat of mixing following equation:

The optimized enthalpies of mixing and interaction

G 0f ( Am Bn ) = a + bT J mol−1 . (17)
coefficients λM =
H /(XMClXNdCl3 ) are shown as lines
in Figs. 1 and 2. Clearly, the results optimized using the The optimized coefficients a and b are listed in Table 3.
new model are in good agreement with experimental data; The measured melting points or peritectic temperatures
typically the enthalpies of mixing have minimum values at (with ∗ ) are also presented in Table 3. It should be
XNdCl3 ≈ 0.4 and the broad minimum values in λM are remembered that all the temperature data are from Ref. [11].
found near XNdCl3 ≈ 0.2. And it should be stressed that
there is no corresponding experimental data for the system 3.3. Calculation
NdCl3 –LiCl.
According to the thermodynamic data optimized above,
3.2.2. Optimized parameters of liquid phases in the the NdCl3 –MCl phase diagrams were calculated by using
NdCl3 –MCl systems a simple computer program. The assessed phase diagrams
In the new approach, the molar energy of A–B pairs, are shown in Figs. 3–7. The solid lines in the figures are

g AB , is a function of the mole fractions of i – j pairs shown calculated. A comparison of the evaluated invariant points
in Eqs. (14) and (15). But different kinds of expressions can and the experimental values for the NdCl3 –MCl binary
be selected, and in this work the Margules [32] expression systems were also given in the Table 4.
Eq. (16) is put to use. It is clear that the calculated phase diagrams are in good
 agreement with the experimental data. There is no solid solu-
j

g AB = X AB X n (C1 + C2 T ) (16) tion between components MCl and NdCl3 . But some crystal
transitions of the intermediate compounds at low tempera-
where n can be AA and BB, while C1 and C2 correspond to ture cannot be calculated, which is indicated by dotted lines.
the enthalpy of mixing and excess entropy, respectively. In
this work j = 0, 1, 2, 4. Table 2 shows all the coefficients 3.4. Discussion
for the NdCl3 –MCl binary systems.
Comparing the five NdCl3 –MCl phase diagrams, we
3.2.3. Intermediate compounds observed that the larger the ionic radius of the alkali metal
The term
G 0f ( Am Bn ) , the Gibbs energy of the formation is, the larger the number of the compounds contained in the
per mole of atoms of the compound, can be expressed by the system is and the greater the stability of these compounds is.
114 Y. Sun et al. / Computer Coupling of Phase Diagrams and Thermochemistry 28 (2004) 109–114

With the larger alkali metal ions, compounds M3 NdCl6 , [3] Y. Sun, Z. Qiao, Rare Metals 21 (1) (2002) 36 (in Chinese).
M2 NdCl5 , MNd2 Cl7 are formed. For the enthalpy of mixing, [4] Y. Sun, Z. Qiao, Y. Zhang, in: Proceeding of 6th International
it becomes more negative from NdCl3 –LiCl to NdCl3 –CsCl. Symposium on Molten Salt Chemistry and Technology, ISBN-81058-
391-3/TQ. 003, p. 314.
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Sr, Ba) [2], CeCl3 –ACl [4] (A = Li, Na, K, Rb, Cs), [6] Y. Sun, Z. Qiao, J. Univ. Sci. Technol. Beijing 21 (5) (1999) 444 (in
LnCl3 –ACl [31] (Ln = Y, La, Ce, Pr; A = Li, Na, K, Rb, Chinese).
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The project was supported by the National Natural 83.
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