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Published by: Sourabh Gour on Sep 24, 2010
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Crystal Structures
Atoms (and later ions) will be viewed as hard spheres. In the case of pure metals, the packing pattern often provides the greatest spatial efficiency (closest packing). Ionic crystals can often be viewed as a closeclosepacked arrangement of the larger ion, with the smaller ion placed in the ´holesµ of the structure.

Unit Cells
Crystals consist of repeating asymmetric units which may be atoms, ions or molecules. The space lattice is the pattern formed by the points that represent these repeating structural units.

Unit Cells
A unit cell of the crystal is an imaginary parallelparallel-sided region from which the entire crystal can be built up. Usually the smallest unit cell which exhibits the greatest symmetry is chosen. If repeated (translated) in 3 dimensions, the entire crystal is recreated.

Close Packing
Since metal atoms and ions lack directional bonding, they will often pack with greatest efficiency. In close or closest packing, each metal packing, atom has 12 nearest neighbors. The number of nearest neighbors is called the coordination number. Six atoms surround an number. atom in the same plane, and the central atom is then ´cappedµ by 3 atoms on top, and 3 atoms below it.

or is said to be hexagonal close packed. packed. in an ABA pattern. the arrangement has a hexagonal unit cell. faceThis arrangement is called cubic close packing. .Close Packing If the bottom ´capµ and the top ´capµ are directly above each other. the unit cell that results is a face-centered cube. If the bottom and top ´capsµ are staggered. packing.

Close Packing .

Small holes make up the other 26% of the unit cell. .Close Packing Either arrangement utilizes 74% of the available space. producing a dense arrangement of atoms.

.Holes in Close Packed Crystals There are two types of holes created by a close-packed closearrangement. Octahedral holes lie within two staggered triangular planes of atoms.

there are n octahedral holes. For n atoms in a closeclose-packed structure. .Holes in Close Packed Crystals The coordination number of an atom occupying an octahedral hole is 6.

. Each hole has a coordination number of 6. The small orange spheres show the position of octahedral holes in the unit cell.Octahedral Holes The green atoms are in a cubic close-packed closearrangement.

414 r where r is the radius of the cubic close-packed closeatom or ion. .Octahedral Holes The size of the octahedral hole = .

The resulting hole has a coordination number of 4.Holes in Close Packed Crystals Tetrahedral holes are formed by a planar triangle of atoms. . with a 4th atom covering the indentation in the center.

The small white spheres behind each corner indicate the location of the tetrahedral holes. .Tetrahedral Holes The orange spheres show atoms in a cubic closeclose-packed arrangement.

225 r where r is the radius of the close-packed atom or closeion. 2n The size of the tetrahedral holes = .Tetrahedral Holes For a close-packed closecrystal of n atoms. . there are 2n tetrahedral holes.

# of Atoms/Unit Cell For atoms in a cubic unit cell: Atoms in corners are within the cell  .

# of Atoms/Unit Cell For atoms in a cubic unit cell:  Atoms on faces are ½ within the cell .

. and 3 from the faces.# of Atoms/Unit Cell A face-centered facecubic unit cell contains a total of 4 atoms: 1 from the corners.

# of Atoms/Unit Cell For atoms in a cubic unit cell:    Atoms in corners are within the cell Atoms on faces are ½ within the cell Atoms on edges are ¼ within the cell .

. The packing efficiency is 68%. and the coordination number = 8.Other Metallic Crystal Structures BodyBody-centered cubic unit cells have an atom in the center of the cube as well as one in each corner.

The coordination number is 6. The atoms occupy the corners of a cube. and the packing efficiency is only 52.Other Metallic Crystal Structures Simple cubic (or primitive cubic) unit cells are relatively rare. .4%.

Higher temperatures often cause closeclosepacked structures to become body-center cubic bodystructures due to atomic vibrations. denser forms occur at higher pressures.Polymorphism Many metals exhibit different crystal structures with changes in pressure and temperature. . Typically.

However. increasing with increasing coordination number. this distance varies with coordination number of the atom.Atomic Radii of Metals Metallic radii are defined as half the internuclear distance as determined by X-ray Xcrystallography. .

000 0.88 .Atomic Radii of Metals Goldschmidt radii correct all metallic radii for a coordination number of 12.97 0.96 0. Coord # 12 8 6 4 Relative radius 1.

Alloys Alloys are solid solutions of metals. . or occur in a fixed ratio. with a uniform distribution. as in a compound with a specific internal structure. They are usually prepared by mixing molten components. They may be homogeneous.

an alloy of zinc and copper.Substitutional Alloys Substitutional alloys have a structure in which sites of the solvent metal are occupied by solute metal atoms. . An example is brass.

2. . 3.Substitutional Alloys These alloys may form if: 1. The electropositive nature of the metals is similar (to prevent a redox reaction). The unit cells of the pure metals are the same. The atomic radii of the two metals are within 15% if each other.

An example is steel.Interstitial Alloys Interstitial alloys are solid solutions in which the solute atoms occupy holes (interstices) within the solvent metal structure. an alloy of iron and carbon. .

. They can be dissolved in a simple whole number ratio (Fe3C) to form a true compound. or randomly distributed to form solid solutions.Interstitial Alloys These alloys often have a non-metallic solute nonthat will fit in the small holes of the metal lattice. Carbon and boron are often used as solutes.

Intermetallic Compounds Some mixtures of metals form alloys with definite structures that may be unrelated to the structures of each of the individual metals. MgZn2. Cu3Au. The metals have similar electronegativities. . and Na5Zn2. and molten mixtures are cooled to form compounds such as brass (CuZn).

ionic structures are often viewed as a closeclosepacked array of anions with cations added. and sometimes distorting the close-packed closearrangement. .Ionic Compounds Since anions are often larger than cations.

or .Common Crystal Types 1. with the cations in all of the octahedral holes. The Rock Salt (NaCl) structurestructureCan be viewed as a faceface-centered cubic array of the anions.

Common Crystal Types 1. The Rock Salt (NaCl) structurestructureA face-centered cubic facearray of the cations with anions in all of the octahedral holes. .

The Rock Salt (NaCl) structurestructureThe coordination number is 6 for both ions.Common Crystal Types 1. .

. Both ions have a coordination number of 8. with the two ions fairly similar in size.Common Crystal Types 2. with a cesium ion in the center (called a cubic hole) or vice hole) versa. The CsCl structurestructureChloride ions occupy the corners of a cube.

. with cations (Zn2+) in half of the tetrahedral holes.Common Crystal Types 3. The Zinc-blende or Sphalerite structureZincstructureAnions (S2-) ions are in a face-centered cubic facearrangement.

Common Crystal Types 4. The Fluorite (CaF2) and Antifluorite structures A face-centered cubic arrangement of Ca2+ faceions with F. .ions in all of the tetrahedral holes.

The Fluorite (CaF2) and Antifluorite structures The antifluorite structure reverses the positions of the cations and anions.Common Crystal Types 4. An example is K2O. .

and not the electrons.40Å). . and the radius of the cation is determined relative to this assigned value. as x-ray xdata only shows the position of the nuclei.Ionic Radii Ionic radii are difficult to determine. Most systems assign a radius to the oxide ion (often 1.

. the apparent ionic radius increases. As the coordination number increases.Ionic Radii Like metallic radii. ionic radii seem to vary with coordination number.

If an ion can be found in many environments. its radius increases with higher coordination number. Ionic radii increase as you go down a group. 5. For cations. the smaller the ion (assuming the same coordination #).Ionic Radii 1. For atoms near each other on the periodic table. the greater the charge. cations are generally smaller than anions. . 4. Radii of ions of similar charge decrease across a period. 2. 3.

Radius ratios. based on unit cell geometry.Predicting Crystal Structures General ´rulesµ have been developed. . to predict crystal structures using ionic radii. usually expressed as the (radius of the cation)/(radius of the anion) are used.

usually expressed as the (radius of the cation)/(radius of the anion) are used. This assumes that the cation is smaller than the anion. .Predicting Crystal Structures General ´rulesµ have been developed. based on unit cell geometry. Radius ratios. to predict crystal structures using ionic radii.

4 -0.7 0.70 0.2 ²0.10 -0.20 unreliable .4 accuracy quite reliable moderately reliable unreliable 0.Predicting Crystal Structures CN 8 6 4 3 r+/r•0.

It is usually defined as the energy change when a mole of a crystalline solid is formed from its gaseous ions. M+(g) + X-(g) MX(s) .Energetics of Ionic Bonds The lattice energy is a measure of the strength of ionic bonds within a specific crystal structure.

They will vary greatly with ionic charge.Lattice Energy M+(g) + X-(g) MX(s) ¨E = Lattice Energy Lattice energies cannot be measured directly. so they are obtained using Hess· Law. . with ionic size. to a lesser degree. and.

1/2 bond energy of Cl2 Ionization energy of K ¨Hsub of K} Electron Affinity of Cl Lattice Energy of KCl ¨Hf of KCl .

Ionic charge has a huge effect on lattice energy. .

602 x 10-19C) 4 o=permittivity of vacuum (1.Lattice Energy Attempts to predict lattice energies are generally based on coulomb·s law: VAB = (Zae)(Zbe) 4 orAB Za and Zb = charge on cation and anion e= charge of an electron (1.1127 x 10-10J-1C2m-1) rAB = distance between nuclei .

next nearest neighbors. etc. the attractive and repulsive forces between neighboring ions..Lattice Energy Since ionic crystals involve more than 2 ions. must be considered. .

but independent of interionic distances or ionic charges.The Madelung Constant The Madelung constant is derived for each type of ionic crystal structure. . It is the sum of a series of numbers representing the number of nearest neighbors and their relative distance from a given ion. The constant is specific to the crystal type (unit cell).

763 2.748 1.641 .638 1.Madelung Constants Crystal Structure Cesium chloride Fluorite Rock salt (NaCl) Sphalerite Wurtzite Madelung Constant 1.519 1.

and assumes 100% ionic bonding. and M is the Madelung constant (sometimes represented by A) This estimate is based on coulombic forces.Estimating Lattice Energy Ec = NM(Z+)( Z-) e2 4 or where N is Avogadro·s number. .

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