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Solids

Solids have resistance to changes in both shape and volume Solids can be Crystalline or Amorphous Crystals are solids that consist of a periodic array of atoms, ions, or molecules
If this periodicity is preserved over large (macroscopic) distances the solid has Longrange Order

Amorphous solids do not have Long-Range Order


Short Range Order

Solids
Crystals Solids:
Short-range Order Long-range Order

Amorphous solids:
~Short-range Order No Long-range Order

Crystals
The periodic array of atoms, ions, or molecules that form the solids is called Crystal Structure Crystal Structure = Space (Crystal) Lattice + Basis
Space (Crystal) Lattice is a regular periodic arrangement of points in space, and is purely mathematical abstraction Crystal Structure is formed by putting the identical atoms (group of atoms) in the points of the space lattice This group of atoms is the Basis

Crystal Structure and Classification of Solids

Crystals
Crystal Structure = Space Lattice + Basis

Solids
Different solids can have the same geometrical arrangements of atoms
Properties are determined by crystal structure, i.e. both crystal lattice and basis are important

Example:
Si, Diamond (C), GaAs, ZnSe have the same geometry Si and C (Diamond) Form Diamond Structure GaAs or ZnSe form a structure called Zinc Blende
http://www.neubert.net/Crystals/CRYStruc.html

Solids
Different arrangements of atoms (even the same atoms) give different properties

Single layer is graphene

Solid Models: Close-Packed Spheres


Most atoms or ions forming solids have spherical symmetry Considering the atoms or ions as solid spheres we can imagine crystals as closely packed spheres

Classification of Solids
Since we know the structure of atoms that form solids, we can classify them via the type of bonds that hold solids together
In this case we say that we classify solids according to the nature of bonding There are four classes of solids:
metallic, ionic, covalent, and molecular

All the forces holding solids together have electrostatic origin

General Considerations
There must be an attractive force
An apparent candidate is the Coulomb Force 1 q1q2 F 4 0 r 2 Here r is a distance between atoms (ions) forming a solid

What stops atoms (ions) from getting closer than they do?
When ions are very close to each other, other forces arise. These are the so-called short-range repulsive forces, due to rearrangement of electrons as nuclei approach

Equilibrium distance, r0, is point at which energy is at a minimum, forces are balanced

General Considerations

Ionic Solids
Ionic crystals consist of the negative and positive ions, attracted to each other
Electron from one of the atoms removed and transferred to another: NaCl, AgBr, KCl

When the crystal is formed excess heat is generated

Crystalline Structure of NaCl

Ionic Solids
Lets find the energy required to transfer an electron from Na to Cl and then to form a NaCl molecule
To remove an electron from Na (ionize the atom) one needs to spend 5.14eV (compare with the ionization energy of a hydrogen atom?)

Na + 5.14eV Na+ + e When a Cl atom captures an electron, 3.62eV of energy is released

Cl + e- Cl- + 3.62eV

Ionic Solids
In solid, Na+ and Cl- are brought together at the distance r0 2.51 [ = 10-10m = 0.1nm]
The total energy is lowered due to the Coulomb attraction 1 e2 The results is -5.73 eV

4 0 r

Thus when a NaCl molecular unit of NaCl solid is formed the following occurs Na + 5.14eV Na+ + eCl + e- Cl- + 3.62 eV Cl- + Na+ NaCl + 5.73 eV Na + Cl NaCl + 4.21 eV

Ionic Solids
The energy gain for NaCl solid is ~ 4.21 eV per NaCl pair
This is the energy required to break an NaCl molecule and restore neutral Na and Cl atoms

This energy is huge (in 1 cm3): 4.211.610-19 (Joules per pair) 3 1022 (pairs) = 20200 Joules
To more accurately calculate the total electrostatic energy, need to calculate interaction of each ion with all other ions in the crystal

Ionic Solids
In ionic crystals all electrons are bound to the ions: There are no free electrons!!!

Thus most ionic crystals are insulators

There are ionic conductors, where ions, and not electrons conduct: Example: AgI

Covalent Solids
The covalent bond is usually formed from two electrons, one from each atom participating in the bonding: These electrons are shared by the atoms
Quantum Mechanics is required to calculate binding energies The probability of finding electrons forming the bond between the two atoms is high Covalent bonds are very strong and directional

Covalent Solids
In general, since there are no free electrons, these crystals are insulators or semiconductors

Crystalline Structure of Diamond

Compare
Covalent Solids

Ionic Solids

Mixed Bonding Solids


The electrons forming the covalent bond tend to be localized in the region between the two atoms If the atoms elements forming the covalent solid are different
e.g., Zn & Se for ZnSe then the electrons a localized closer to one of the atoms (with higher electron affinity)

We say that the bond is partially covalent and partially ionic

Metallic Bond
Metals may be seen as collections of stationary ions surrounded by a sea of electrons
Can be viewed as limit of covalent bonding, when electrons are shared by all the ions in the crystal The metallic bond is not directional

Molecular Solids

Very weak bonding: Dipole-Dipole Interaction

U
Liquid Crystals, Ice

r6

low melting temperatures

Classification of Solids by Conductivity


Another way of classifying solids, in addition to (a) crystal structure and (b) type of bonds between atoms is (c) electrical conductivity Conductors Insulators Semiconductors