Lanthanide carbides

Many of the binary compounds of the lanthanides, such as oxides, nitrides, and carbides, can exist as non stoichiometric compounds. These form crystals where some of the anions ate missing from the sites the anions normally occupy. 

If pure, the carbides of Groups 1 and 2 are characterized by their transparency and lack of conductivity. The carbides of Group 3, ie. Sc, Y, the lanthanides, and the actinides, ate opaque. Some, depending on composition, show metallic luster and electroconductivity. The cation may exist in the MC2 phases of this group, and the remaining valence electron apparendy imparts pardy metaUic character to these compounds. 

The lanthanides (from La to Lu) and yttrium form isomorphous dicarbides with a structure of the CaC2 type (body-centered tetragonal). These lanthanide carbides are known to have conduction electrons (one... 

The main difficulty is to prevent pyrohydrolysis over the long experimental periods. (Moisture is removed by "gettering with hot lanthanides or actinides.) The potentials of M/MF reference electrodes have also been used to study activities of metals in alloys, carbides, and borides (208). The accuracy is limited by reproducibility of potentials (2 1 mV) as a fraction of the cell potential and indeterminate errors. The latter can be avoided by checking for internal consistency (e.g., measuring emfs of two cells against a common third electrode). 

The yield and rate of the tantalothermic reduction of plutonium carbide at 1975 K are given in Fig. 3. Producing actinide metals by metallothermic reduction of their carbides has some interesting advantages. The process is applicable in principle to all of the actinide metals, without exception, and at an acceptable purity level, even if quite impure starting material (waste) is used. High decontamination factors result from the selectivities achieved at the different steps of the process. Volatile oxides and metals are eliminated hy vaporization during the carboreduction. Lanthanides, Y, Ti, Zr, Hf, V, Nb, Ta, Mo, and W form stable carbides, whereas Rh, Os, Ir, Pt, and Pd remain as nonvolatile metals in the actinide carbides. Thus, these latter elements... 

As we go from left to right across the transition metals in the periodic table, the metal atoms become smaller, much as in the lanthanide contraction (Section 2.6). Furthermore, the atoms of elements of the first transition series are smaller than those of corresponding members of the second and third. Consequently, interstitial carbides are particularly important for metals toward the lower left of the series, as with TiC, ZrC, TaC, and the extremely hard tungsten carbide WC, which is used industrially as an abrasive or cutting material of almost diamond like hardness. The parallel with trends in chemisorption (Section 6.1) will be apparent. 

A common precursor to LnN are the simple inorganic amides Ln(NH2)x (x = 2, 3) which can be placed between the nitrides and the alkyl substituted amides. Their main use lies in the synthesis of other solid materials like lanthanide hydroxides [21,33], carbides [34] or above-mentioned nitrides. Very recently solutions of europium and ytterbium in liquid ammonia have been rediscovered as synthetic tools (Sect. 7.1). 

From the early 1960s onwards, the use of lanthanide (Ln) based catalysts for the polymerization of conjugated dienes came to be the focus of fundamental studies [31]. The first patent on the use of lanthanides for diene polymerization originates from 1964 and was submitted by Union Carbide Corporation (UCC) [32,33]. In this patent the use of binary lanthanum and cerium catalysts is claimed. Soon after this discovery by UCC, Throckmorton (Goodyear) revealed the superiority of ternary lanthanide catalyst systems over binary catalyst systems. The ternary systems introduced by Throckmorton comprise a lanthanide compound, an aluminum alkyl cocatalyst and a halide donor [34], Out of the whole series of lanthanides Throckmorton... 

Various borides, sulfides, carbides, nitrides, etc., have been obtained by direct interaction of the elements at elevated temperatures. Like other actinide and lanthanide metals, thorium also reacts at elevated temperatures with hydrogen. Products with a range of compositions can be obtained, but two definite phases, ThH2 and TlqH, have been characterized. 

Pnictides LnQ (Q = Group 15 element) having the NaCl structure are made by direct synthesis, with other routes for the nitrides including the reaction of the lanthanide hydride with either nitrogen or aimnonia hke the carbides, they are readily hydrolyzed to the hydride QH3. 

---