大学化学(非专业)第7章固态(e)教学课件.pptVIP

* * Chemistry Department of Fudan University Pauling Rule 4: Cation Evasion in Binaries In a crystal containing different cations those of high valency and small coordination number tend not to share polyhedron elements with each other CaII 12-coordinate CaO12 cuboctahedra share FACES TiIV 6-coordinate TiO6 octahedra share only VERTICES * * Chemistry Department of Fudan University Pauling Rule 5: Environmental Homogeneity The number of essentially different kinds of constituent in a crystal tend to be small i.e. as far as possible, similar environments for chemically similar atoms Treating the mineral Garnet Ca3Al2Si3O12 as an ionic crystal Ca2+ Al3+ Si4+ coordination 8 6 4 e.b.s. 1/4 1/2 1 O2- bond strength of 2 is satisfied by a number of alternative combination of bonds Pauling Rule 5: Each O2- would prefer the same environment Only one possible arrangement: * * Chemistry Department of Fudan University When Paulings Rules are NOT Obeyed ???Special structural influences in the bonding Face-sharing Distorted coordination polyhedra * * Chemistry Department of Fudan University Indirect evidence that the structure is NOT ionic Increasing Polarization in bonding low-dimensionality - layers/chains * * Chemistry Department of Fudan University P=4, Tectosilicate, SiO2 e.g. Mn+x/n[(AlO2)x(SiO2)y].mH2O Zeolite ZSM-5 * * Chemistry Department of Fudan University CARBON with P = 4 the Diamond FRAMEWORK * * Chemistry Department of Fudan University Types of Solids: Example Crystalline Structures Diamond Tetrahedral sp3 bonding (very hard!) Graphite Planar sp2 bonding (good lubricant) Vertical p-bonds Bond angle = 109.5o * * Chemistry Department of Fudan University Valence type of crystal diamond AB → ZnS, AgI, CuX, SiC, ZnO AB2 → SiO2, GeO, BeF2 * * Chemistry Department of Fudan University Mixing type of crystal Graphite CaI2 * * Chemistry Department of Fudan University Hydrogen bond type of crystal Ice * * Chemistry Depar