Thermodynamic Description of the ACl-ThCl4 (A = Li, Na, K) Systems
Abstract
:1. Introduction
2. Thermodynamic Modelling
2.1. Pure Compounds
2.2. Liquid Solution
3. Results and Discussion
3.1. Phase Diagrams
3.2. Enthalpy of Mixing
4. Conclusions
- Isolate the intermediate phases LiThCl, NaThCl, and KThCl and elucidate their crystal structures;
- Derive their standard enthalpies of formation and standard entropies;
- Obtain novel phase equilibrium data with calorimetry, particularly for the KCl-ThCl system;
- Measure enthalpies of mixing for the liquid solutions.
Author Contributions
Funding
Conflicts of Interest
References
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System | Compounds | References |
---|---|---|
LiCl-ThCl | LiThCl | [20,21,23] |
none | [19] | |
NaCl-ThCl | NaThCl | [19,20,21] |
NaThCl | [23] | |
KCl-ThCl | KThCl | [19,24] |
KThCl | [21,24] | |
KThCl | [19,24] |
Compound | H(298 K)/ (kJ·mol) | S(298 K)/ (J·Kmol) | C(T/K)/(J·Kmol) = a + b·T + c·T + d·T | Range | Reference | |||
---|---|---|---|---|---|---|---|---|
a | b | c | d | |||||
LiCl(cr) | −408.266 | 59.3 | 44.70478 | 0.01792765 | 1.863482 × 10 | −194,457.7 | 298–883 | [27] |
73.30619 | −0.009430108 | 33,070.5 | 883–2000 | [27] | ||||
LiCl(l) | −388.4342 | 81.76 | 44.70478 | 0.01792765 | 1.863482 × 10 | −194,457.7 | 298–883 | [27] |
73.30619 | −0.009430108 | 33,070.5 | 883–2000 | [27] | ||||
NaCl(cr) | −411.260 | 72.15 | 47.72158 | 0.0057 | 1.21466 × 10 | −882.996 | 298–1074 | [28] |
NaCl(l) | −390.853 | 83.302 | 68.0 | 298–2500 | [28,29] | |||
KCl(cr) | −436.6841 | 82.555 | 50.47661 | 0.005924377 | 7.496682 × 10 | −144,173.9 | 298–700 | [27] |
143.5698 | −0.1680399 | 9.965702 × 10 | −8,217,836 | 700–1044 | [27] | |||
73.59656 | −8,217,836 | 1044–2000 | [27] | |||||
KCl(l) | −410.4002 | 107.7311 | 50.47661 | 0.005924377 | 7.496682 × 10 | −144,173.9 | 298–700 | [27] |
143.5698 | −0.1680399 | 9.965702 × 10 | −8,217,836 | 700–1044 | [27] | |||
73.59656 | 1044–2000 | [27] | ||||||
-ThCl(cr) | −1191.3012 | 176.135 | 120.293 | 0.0232672 | −615,050 | 298–1042 | this work, [35] | |
-ThCl(cr) | −1186.300 | 183.499 | 120.293 | 0.0232672 | −615,050 | 298–1042 | [5,34] | |
ThCl(l) | −1149.740 | 197.626 | 167.4 | 298–1500 | [5,34] | |||
LiThCl(cr) | −2834.966 | 413.34 | 299.11212 | 0.0949778 | 7.453928 × 10 | −1,392,880.8 | 298–883 | this work |
413.51776 | −0.014453232 | −482,768 | 883–1042 | |||||
437.1957 | −0.037720432 | 132,282 | 1042–2000 | |||||
NaThCl(cr) | −2051.540 | 328.0 | 215.73616 | 0.0346672 | 2.42932 × 10 | −616,815.992 | 298–1042 | this work |
239.41 | 0.0114 | 2.42932 × 10 | −1765.992 | 1042–1074 | ||||
KThCl(cr) | −1685.000 | 258.69 | 170.76961 | 0.029191577 | 7.496682 × 10 | −759,223.9 | 298–700 | this work |
263.8628 | −0.1447727 | 9.965702 × 10 | −8,832,886 | 700–1042 | ||||
287.5408 | −0.1680399 | 9.965702 × 10 | −8,217,836 | 1042–1044 | ||||
217.568 | 1044–2000 | |||||||
KThCl(cr) | −2139.850 | 380.5 | 221.24622 | 0.035115954 | 1.4993364 × 10 | −903,397.8 | 298–700 | this work |
407.4326 | −0.3128126 | 1.9931404 × 10 | −17,050,722 | 700–1042 | ||||
431.1106 | −0.3360798 | 1.9931404 × 10 | −16,435,672 | 1042–1044 | ||||
291.16408 | 1042–2000 |
A | B | Z | Z |
---|---|---|---|
Li | Li | 6 | 6 |
Na | Na | 6 | 6 |
K | K | 6 | 6 |
Th | Th | 6 | 6 |
Li | Th | 4 | 6 |
Na | Th | 3 | 6 |
K | Th | 4 | 6 |
System | Equilibrium | Invariant Reaction | This Study (calc.) | Tanii et al. [21] | Vokhmyakov et al. [20] | Oyamada [19] | ||||
---|---|---|---|---|---|---|---|---|---|---|
X(ThCl) | T / K | X(ThCl) | T / K | X(ThCl) | T / K | X(ThCl) | T / K | |||
LiCl-ThCl | Congruent Melting | LiCl = L | 1 | 883 | 1 | 881 | 1 | 910 | ||
Peritectic | LiThCl = LiCl + L | 0.2 | 723 | 0.2 | 725 | 0.2 | 723 | - | - | |
Eutectic | LiThCl + -ThCl = L | 0.343 | 695 | - | 690 | 0.38 | 681 | 0.35 | 703 | |
- transition | -ThCl = -ThCl | 1 | 679 | |||||||
Congruent Melting | -ThCl = L | 1 | 1042 | 1 | 1041 | 1 | 1070 | |||
NaCl-ThCl | Congruent melting | NaCl = L | 0 | 1074 | 0 | 1074 | 0 | 1097 | ||
Eutectic | NaCl + NaThCl = L | 0.251 | 657 | - | 639 | 0.255 | 633 | 0.26 | 667 | |
Congruent Melting | NaThCl = L | 1/3 | 703 | 1/3 | 708 | 1/3 | 708 | 1/3 | 729 | |
Eutectic | NaThCl + -ThCl = L | 0.457 | 654 | - | 637 | 0.45 | 648 | 0.49 | 686 | |
KCl-ThCl | Congruent melting | KCl = L | 0 | 1044 | 0 | 1043 | 0 | 1070 | ||
Eutectic | KCl + KThCl = L | 0.206 | 894 | - | 895 | 0.25 | 903 | 0.15 | 917 | |
Congruent melting | KThCl = L | 1/3 | 977 | 1/3 | 988 | 1/3 | 978 | 0.25 | 997 | |
Eutectic | KThCl + KThCl = L | 0.467 | 697 | - | 705 | 0.42 | 668 | 0.43 | 681 | |
Congruent melting | KThCl = L | 0.5 | 702 | 0.5 | 703 | 0.5 | 741 | |||
Eutectic | KThCl + -ThCl = L | 0.536 | 699 | 0.54 | 693 | 0.56 | 706 |
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Ocádiz Flores, J.A.; Rooijakkers, B.A.S.; Konings, R.J.M.; Smith, A.L. Thermodynamic Description of the ACl-ThCl4 (A = Li, Na, K) Systems. Thermo 2021, 1, 122-133. https://doi.org/10.3390/thermo1020009
Ocádiz Flores JA, Rooijakkers BAS, Konings RJM, Smith AL. Thermodynamic Description of the ACl-ThCl4 (A = Li, Na, K) Systems. Thermo. 2021; 1(2):122-133. https://doi.org/10.3390/thermo1020009
Chicago/Turabian StyleOcádiz Flores, Jaén A., Bas A. S. Rooijakkers, Rudy J. M. Konings, and Anna Louise Smith. 2021. "Thermodynamic Description of the ACl-ThCl4 (A = Li, Na, K) Systems" Thermo 1, no. 2: 122-133. https://doi.org/10.3390/thermo1020009