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    7 Crystal Structure and Classification of Solids

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    Rini Sukkie
    Solids can be crystalline or amorphous. Crystalline solids have long-range order with a periodic array of atoms, while amorphous solids only have short-range order. Crystal structure is defined by the space lattice and basis. Solids are classified based on the nature of bonding between atoms - metallic, ionic, covalent, or molecular. Ionic solids consist of positive and negative ions held together by electrostatic attraction, while covalent solids have electrons shared between atoms through covalent bonds.

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    7 Crystal Structure and Classification of Solids

    Uploaded by

    Rini Sukkie
    277 views25 pages
    Solids can be crystalline or amorphous. Crystalline solids have long-range order with a periodic array of atoms, while amorphous solids only have short-range order. Crystal structure is defined by the space lattice and basis. Solids are classified based on the nature of bonding between atoms - metallic, ionic, covalent, or molecular. Ionic solids consist of positive and negative ions held together by electrostatic attraction, while covalent solids have electrons shared between atoms through covalent bonds.

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    Solids can be crystalline or amorphous. Crystalline solids have long-range order with a periodic array of atoms, while amorphous solids only have short-range order. Crystal structure is defined by the space lattice and basis. Solids are classified based on the nature of bonding between atoms - metallic, ionic, covalent, or molecular. Ionic solids consist of positive and negative ions held together by electrostatic attraction, while covalent solids have electrons shared between atoms through covalent bonds.

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    Attribution Non-Commercial (BY-NC)
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    277 views25 pages

    7 Crystal Structure and Classification of Solids

    Uploaded by

    Rini Sukkie
    Solids can be crystalline or amorphous. Crystalline solids have long-range order with a periodic array of atoms, while amorphous solids only have short-range order. Crystal structure is defined by the space lattice and basis. Solids are classified based on the nature of bonding between atoms - metallic, ionic, covalent, or molecular. Ionic solids consist of positive and negative ions held together by electrostatic attraction, while covalent solids have electrons shared between atoms through covalent bonds.

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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

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