Rare earth carbides R{sub 4}C{sub 5} with R = Y, Gd, Tb, Dy, and Ho
- Universite Muenster (Germany); and others
The five carbides R{sub 4}C{sub 5} (R = Y, Gd-Ho) have been prepared by arc-melting cold-pressed pellets of the elemental components and subsequent annealing at 1050{degrees}C. They crystallize with a new orthorhombic structure type (Pbam, Z = 2), which has been determined from X-ray powder diffractometer data of Y{sub 4}C{sub 5} (a = 657.35(9) pm, b = 1191.8(1) pm, c = 366.92(5) pm, R{sub F} = 0.035 for 179 structure factors) and also refined from powder data of Tb{sub 4}C{sub 5} (a = 660.8(1) pm, b = 1197.3(2) pm, c = 368.71(6) pm, R{sub F} = 0.035 for 181 F values) and Ho{sub 4}C{sub 5} (a = 653.00(8) pm, b = 1184.6(1) pm, c = 363.80(4) pm, R{sub F} = 0.036 for 171 F values and 10 positional parameters each). The structure contains building blocks, which were also found in the two closely related structures of {alpha}- and {beta}-Ho{sub 4}C{sub 7}. One-fifth of the carbon atoms are isolated from each other and coordinated octahedrally by rare earth atoms. The other carbon atoms form pairs with C-C bond distances of 133.5(15), 136(3), and 129(2) pm in Y{sub 4}C{sub 5}, Tb{sub 4}C{sub 5}, and Ho{sub 4}C{sub 5}, respectively, corresponding to C-C double bonds. Hence, all valence electrons can be accommodated in bonding R-C and C-C states according to the formula (R{sup +3}){sub 4}(C{sub 2}{sup -4}){sub 2}C{sup -4}, where the superscripts represent oxidation numbers. Nevertheless, the hydrolysis of Y{sub 4}C{sub 5} and Ho{sub 4}C{sub 5} with distilled water resulted in up to 41 wt% ethane, up to 16 wt% propane and propene, and up to 18 wt% higher hydrocarbons in addition to the expected products methane and ethylene.
- OSTI ID:
- 569685
- Journal Information:
- Journal of Solid State Chemistry, Vol. 132, Issue 2; Other Information: PBD: Sep 1997
- Country of Publication:
- United States
- Language:
- English
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