Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Discussed about atoms and how they bond Moving into the arrangements of atoms and how they form a structure Crystallinity and Non-Crystallinity
Crystalline Materials
Crystal: A solid with atoms arranged in a repeating or periodic array over large atomic distances Long range order exists Repetitive 3-D pattern Each atom is bonded to its nearest-neighbor atoms Simple arrangement for metals, extremely complex for polymers and ceramics Properties depend on the spatial atomic arrangement
Li3N
Local arrangement of atoms in a solid is usually predictable This may be in long range repeating structure Crystalline This may be in short irregular sections Amorphous or Glassy Arrangement depends on bond
atoms pack in periodic, 3D arrays typical of: -metals -many ceramics -some polymers
Crystalline materials
crystalline SiO2
Adapted from Fig. 3.41(a), Callister & Rethwisch 4e.
Non-Crystalline materials
Si
Oxygen
atoms have no periodic packing occurs for: -complex structures -rapid cooling "Amorphous" = Noncrystalline
noncrystalline SiO2
Adapted from Fig. 3.41(b), Callister & Rethwisch 4e. 5
Terminology
Atomic Hard Sphere Model: Atoms are thought of as hard spheres with well defined diameters
Lattice: 3-D array of points coinciding with the atom positions (sphere centers) Unit Cell: The smallest repeating entities in a crystal structure
Crystal Systems
A vast array of possible crystal structures Convenient to divide them into groups based on cell configurations or atomic arrangements Most common based on Unit Cell Geometry Defining the unit cell geometry in terms of six parameters 3 edge lengths and 3 interaxial angles Crystals having seven possible combinations of edge lengths and interaxial angles
Metallic bonding Non-directional Typically, all atomic radii are the same Large number of nearest neighbor atoms, leading to a high packing density Three crystal structures observed in general:
Face-Centered Cubic (FCC) Body-Centered Cubic (BCC) Hexagonal Close Packed (HCP)
Simple Cubic
More Terminology
Co-Ordination Number: The number of nearest neighbor, or touching atoms Atomic Packing Factor (APF): Fraction of solid sphere volume in a unit cell (assuming the atomic hard sphere model)
APF Volume of atoms in unit cell Total volume of the unit cell
APF = 0.52
Co-ordination number - 6
Atoms located at the eight corners, and one at the center of the cube Equivalent of one atom from the eight corners, and one atom at the center 2 atoms in a unit cell Co-ordination number : 8
4 1/8 s ahead 4 1/8 s behind Total 8 neighbors
Hard-Sphere Model
a
2a
APF = 0.68
Atoms located at the eight corners, and the centers of all the cube faces Corner atom is shared among eight unit cells, facecentered atoms among two unit cells 4 atoms in a unit cell Co-ordination number : 12
APF = 0.74
C B
B C B B
A B C
19
Atoms located at top and bottom hexagonal faces, and at center of the faces 3 atoms provided by the plane between the two faces 6 atoms in a unit cell Ideal c/a ratio 1.633 Co-ordination number : 12 APF : 0.74
3D Projection
A sites
c
2D Projection
Top layer Middle layer Bottom layer
B sites
A sites
a
Adapted from Fig. 3.3(a), Callister & Rethwisch 4e.
r0
Interatomic spacing
Typical energy
Interparticle Energy
r0
Interatomic spacing
Typical energy
Theoretical Density ()
Copper FCC Structure, A = 63.5 g/mol, r=0.128 nm = 0.128 * 10-7 cm n=4 (since FCC structure)
4(atoms/unit cell) * 63.5 (g/mol) 16 2 * (0.128 *10 7 ) 3 (cm 3 / unit cell ) * 6.023 *10 23 (atoms/mol)
8.89 g / cm3
More complex than metals since two or more elements present Bonding can vary from purely ionic to purely covalent, and many in between If dominantly ionic bonding, crystal structures have electrically charged ions instead of atoms Cations positively charged (lost electrons) Anions negatively charged (gained electrons)
stable
CaF 2 :
A m Xp
m, p values to achieve charge neutrality
26
a 2ranion
Bond Hybridization
Bond Hybridization is possible when there is significant covalent bonding hybrid electron orbitals form For example for SiC
29
NaCl, MgO, FeO CsCl ZnS, SiC CaF2, UO2 BaTiO3 MgAl2O4
8 4 8 12, 6 4,6
8 4 4 6 4
Answer:
rNa/rCl = 0.564
cations (Na+) prefer octahedral sites
32
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende Cesium Chloride structure:
rCs + rCl-
33
35
n (AC AA ) VC N A
'
n = number of formula units (all ions that are included in the chemical formula) within the unit cell AC = sum of atomic weights of all cations in the formula unit AA = sum of atomic weights of all anions in the formula unit Vc = unit cell volume NA = avogadros number = 6.023 * 1023 formula units/mol
Compute theoretical density of NaCl ANa = 22.99 g/mol; ACl = 35.45 g/mol Ionic radii of Na+ = 0.102 nm, that of Cl- = 0.181 nm
a Na+
Cl-
Polymorphism some metals and non metals have more than one crystal structure
Carbon polymorphs as Diamond and Graphite Pure ion has a BCC crystal structure at room temperature and FCC at 912oC