RARE EARTH CARBIDES

PRESENTED BY-
SWAGAT DAS

INDIAN INSTITUTE OF TECHNOLOGY, GANDHINAGAR

CONTENTS :-

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 1. RARE EARTH ELEMENTS:
• The 17 rare earth elements are :

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1. Scandium (Sc) 21
2. Yttrium (Y) 39
3. Lanthanum (La) 57
Elements with low atomic numbers
4. Cerium (Ce) 58 are referred to as light rare-earth
5. Praseodymium (Pr) 59 elements. Rare-earth elements
6. Neodymium (Nd) 60 with atomic numbers 57 to 61 are
classified as light.
7. Promethium (Pm) 61
8. Samarium (Sm) 62
9. Europium (Eu) 63
10. Gadolinium (Gd) 64
11. Terbium (Tb) 65 Elements with atomic numbers
12. Dysprosium (Dy) 66 greater than 62 (corresponding to
13. Holmium (Ho) 67 europium) are classified as heavy-rare
earth elements.
14. Erbium (Er) 68
15. Thulium (Tm) 69
16. Yatterbium (Yb) 70
17. Letetium (Lu) 71
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2.THERMODYNAMIC PROPERTIES OF RARE EARTH CARBIDES:
Sl.no Species Enthalpy of Gibbs energy of Entropy of
formation formation formation
(-ΔfHo298) (-ΔfGo298) (ΔfSo298)
( kJ/mol ) ( kJ/mol ) (J/mol . K )

1 LaC2(s) 28.4 32.76 14.64

2 CeC2(s) 29.0 38.77 32.77
3 PrC2(s) 28.2 38.41 34.27
4 NdC2(s) 28.0 37.93 33.32
5 SmC2(s) 25.4 35.23 32.97
6 EuC2(s) 22.4 33.0 35.56
7 GdC2(s) 35.2 44.82 32.27
8 DyC2(s) 31.4 41.71 34.59
9 HoC2(s) 28.5 38.82 34.63
10 ErC2(s) 28.1 38.24 34.02

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Cont..
Sl.no Species Enthalpy of Gibbs energy of Entropy of
formation formation formation
(-ΔfHo298) (-ΔfGo298) (ΔfSo298)
( kJ/mol ) ( kJ/mol ) (J/mol . K )

11 TmC2(s) 32.9 43.12 34.29

12 YbC2(s) 25.1 33.91 29.57
13 LuC2(s) 39.1 47.03 26.61
14 YC2(s) 34.4 41.68 24.43
15 La2C3(s) 38.63 36.23 -8.06
16 Ce2C3(s) 35.33 37.24 13.59
17 Pr2C3(s) 27.97 32.55 15.38
18 Nd2C3(s) 34.09 38.33 14.24
19 Sm2C3(s) 37.0 41.06 13.61
20 Ho2C3(s) 11.6 16.31 15.8

Table 1 :Enthalpy, Entropy, and Gibbs Energy of Formation of Solid REC2 and Some Solid RE2C3 Phases at 298 K
(Ref: K.A. Gschneidner,Jr. and F.W Calderwood, Lowa State University,1986,Bulletin of alloy phase diagram.
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 • The entropy of formation values shown for Dicarbides were calculated using the known value of
23.43 KJ/mol.K for CaC2 and assuming the validity of the relationship,
S(REC2) = S(CaC2) + S(RE) – S(Ca)
• A similar calculation was performed to obtain S(RE2C3), based on a value of 15.82 J/mol. K for Ho2C3
• Calculations for S (RE2C3) were based on the relationship S(RE2C3) = S(Ho2C3) + 2S(RE) - 2S(Ho).

(Ref: K.A. Gschneidner,Jr. and F.W Calderwood, Lowa State University,1986,Bulletin of alloy phase diagram.

• According to Leiming Ji et.al. values of thermodynamic functions for CaC2 are:

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3.Cp values of Rare earth Carbide :

• The heat capacity and enthalpy of the rare earth borides and carbides of the cerium subgroup and gad-
olinium in the temperature range 60-2300 K.
Compound Cp
LaC2 66.30
PrC2 78.00
NdC2 73.91
SmC2 67.22
GdC2 59.25
La2C3 105.26
Pr2C3 120.77
Nd2C3 122.35
Sm2C3 125.08
Gd2C3 103.56

Table 2: Heat capacity of rare earth carbides at 298.15k

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 Compound Tm(K) A(*103) B C -D -E
α-LaC2 1369 1.575 71.84 575996 23491 340.95

α-PrC2 1425 3.159 79.11 266373 24762 377.42

α-NdC2 1436 2.410 78.48 533563 25401 370.60

α-SmC2 1455 4.925 85.33 1870949 32154 415.63

α-GdC2 1529 3.110 74.07 1482546 27334 380.98

β-LaC2 1900 10.714 61.49 -3887632 6245 277.72

β-PrC2 2293 5.237 89.48 -346340 25988 446.36

β-NdC2 2095 3.068 96.88 3666096 41454 495.76

β-SmC2 2067 4.930 97.55 453096 31041 492.10

β-GdC2 2278 3.676 91.02 3627838 39633 476.75

La2C3 1633 20.107 104.35 985031 36203 479.73

Pr2C3 1815 24.913 111.73 517188 37262 496.53

Nd2C3 1892 23.328 112.04 320346 36554 485.83

Sm2C3 1480 19.088 129.32 1388570 44910 601.75

Gd2C3 1740 16.475 109.35 1387800 38721 459.80

TABLE 3. Temperature dependence parameters of the enthalpy (J /mol), heat capacity, entropy and free
energy function (J/mol.K) of the rare earth carbides

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• Experimental data for the enthalpy were approxi- mated using the Mayer-Kelly equation:
H°(T) - H ° (298.15 K) = AT2+BT+CT-I +D
• The parameters in eqn. were estimated by the least- square-root method with two boundary conditions:
(1) H°(T)-H ° (298.15K)=0 at 298.15 K and
(2) The heat capacity values at 298.15 K.
• The temperature dependences of heat capacity, entropy and the free energy function are as follows:

Cp(T) = 2AT + B - CT -2
S°(T) = 2AT + B In T + O.5CT-2 + E
ɸ(T) = AT + B In T - DT-I - O.5CT-I + E- B

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4. Magnetic Properties of Rare earth carbide:

Fig: Thermomagnetic analysis of Sm2Fe17C0.5 Fig: Curie temperature as a function of

for several annealing times carbon context (x) in Sm2Fe17Cx
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Fig: Magnetization curves parallel (open circles) and Fig: Concentration dependence of the anisotropy
perpendicular (x) to the alignment direction for constant K1 in Sm2Fe17Cx.
Sm2Fe 17C0.25 and Sm2Fe17C at room temperature.

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 Fig: Thermomagnetic scans for R2Fe17Cx, where R =
Ce, Dy, or Y (Liao et al., 1992).

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Fig: Susceptibility of lanthanon dicavbides as a
function of absolute temperature

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