Isostructural temperature

The molecular and bulk properties of the halogens, as distinct from their atomic and nuclear properties, were summarized in Table 17.4 and have to some extent already been briefly discussed. The high volatility and relatively low enthalpy of vaporization reflect the diatomic molecular structure of these elements. In the solid state the molecules align to give a layer lattice p2 has two modifications (a low-temperature, a-form and a higher-temperature, yS-form) neither of which resembles the orthorhombic layer lattice of the isostructural CI2, Br2 and I2. The layer lattice is illustrated below for I2 the I-I distance of 271.5 pm is appreciably longer than in gaseous I2 (266.6 pm) and the closest interatomic approach between the molecules is 350 pm within the layer and 427 pm between layers (cf the van der Waals radius of 215 pm). These values are... 

Products of the high temperature (typically 750-850°C) reduction of ZrX4 (X = Cl, Br, I) with Zr metal in various proportions, have provided intriguing structural problems. Black phases initially thought to be ZrX2 and made up of ZrgXi2 clusters, isostructural with the well-known [M6Xi2]"+ clusters of Nb and Ta, (p. 992), were subsequently shown to contain... 

In the solid state all three elements have typically metallic structures. Technetium and Re are isostructural with hep lattices, but there are 4 allotropes of Mn of which the o-fomi is the one stable at room temperature. This has a bcc structure in which, for reasons which are not clear, there are 4 distinct types of Mn atom. It is hard and brittle, and noticeably less refractory than its predecessors in the first transition series. 

Wherever possible, we have sought a direct comparison of the reactivities of structurally related Crni and q-II alkyls with ethylene. For example, after having established the catalytic activity of complexes of the type [( Cri (L)2R] (see above), we showed that the isostructural neutral compounds Cp Crn(L)2R did not polymerize ethylene instead facile P-hydrogen elimination was observed. [3) This difference in reactivity was not due to the charge of the complexes. Thus, we have subsequently shown that neutral Cr J alkyls are also active polymerization catalysts. For example, Cp Cr I(THF)Bz2 and even anionic Li[Cp Cr H(Bz)3] (Bz = benzyl) polymerized ethylene at ambient temperature and pressure, while the structurally related CpCrD(bipy)Bz proved inert.[5]... 

The reports about the crystal structure of Mn(Et2cftc)2, determined by means of X-ray powder diagrams are contradictory. According to Fackler and Holah (18) this compound is isomorphous with Cu(Et2rftc)2, but Lahiry and Anand (44) state the complex to be isostructural with Ni(Et2 tc)2- EPR data (g = 1.92 and g = 4.11) and magnetic susceptibility measurements (4.1 BM at room temperature) show the compound to be the first Mn(II) complex with a quartet ground state (44). 

Ishikawa etal. proposed an approach for the determination of the ligand-field (LF) parameters of a set of isostructural lanthanide complexes. This method consists of a simultaneous fit of the temperature dependence of magnetic susceptibilities and NMR spectra for the whole isostructural series [18]. In order to avoid over-parametrization a key restriction is imposed each parameter is expressed as a linear function of the number of f electrons, n ... 

Another important group of oxide materials with a very low electrical conductivity is the oxide dielectrics. A number of these are based upon the perovskites, MXO3 or M0 X02. The archetype of these materials is BaTiC>3, which has a high dielectric constant, or relative permittivity to vacuum, the value at room temperature being 1600, and commercial use is made of the isostructural PbTi(>3 and ZrTi03 which form solid solutions, the PZT dielectrics. These materials lose their dielectric properties as the temperature... 

Figure 2.30. Typical one-component systems (a) Room temperature, room pressure region of the well-known PIT phase diagram of water (notice the logarithmic scale of pressure), (b) P-T phase diagram of elemental Fe. The fields of existence of the different forms of Fe are shown a (body-centred cubic Fe), (face-centred cubic), 6 (body-centred cubic, high-temperature form isostructural with a), e (hexagonal close packed), L (liquid Fe). The gas phase field, owing to the pressure scale and the not very high temperatures considered, should be represented by a very narrow region close to the T axis.

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