The Modern Periodic Table name & atomic mass numberweight symbol atomic number Carbon 12.011 12 6 C Law of Periodicity Group Similar chemical properties “The properties of the elements are periodic functions of atomic number.” Period Repetition of properties Nonmetals – insulators not ductile Metalloids - Semiconductors Ductile ? Metals – Conducting, Ductile Crystalline Solids Crystalline solids: Metals, ions, atoms, molecules Constructed form crystal lattices. Stabilized by electrostatic forces. Identical building blocks : unit cells. LATTICE: 4 X-ray Diffraction X-ray diffraction is used to study crystalline solids The lattice of regularly repeating atoms with spacing acts as a diffraction grating for the rays. The diffraction pattern is used to establish the structure of the solid! Amorphous Solids Amorphous solids: disordered solids Strongly resemble liquids in this lack of long-range order Many amorphous solids can be thought of very accurately as frozen liquids. Common examples of amorphous solid are glass, candy (sugar), plastics. In all, there are then 5 categories of solids, 4 types of crystalline + amorphous Summary of the Structures and Properties of Various Types of Solid Substances Type Examples Structural Units Typical Properties Ionic NaCl, K2SO4, CaCl2, (NH4)3PO4 Positive and negative ions Hard; brittle; high melting point; electric conductivity poor as solid & good as liquid; often water-soluble Metallic Iron, silver, copper, other metals & alloys Metal cations in a sea of electrons Malleable; ductile; wide range of hardness and melting points; good electric conductivity in solid & liquid; good heat conductivity. Molecular H2, O2, I2, H2O, CO2, CH4, CH3OH, CH3CO2H Molecules Soft; low to moderate melting points & boiling points; poor electric conductivity in solid and liquid Network Graphite, diamond, quartz, feldspars, mica Atoms Wide range of hardnesses & melting points (3-dimensional bonding > 2dimensional bonding > 1-dimensional bonding); poor electric conductivity, with some exceptions Amorphous (glassy) Glass, polyethylene, nylon Molecules, ions No long range order Soft, wide temperature range for melting; poor electric conductivity, with some exceptions Semicrystalline Materials Contain both amorphous and crystalline regions => strong and flexible. Examples: Plastics (polymers), Steel, Wood (cellulose), collagen (tendon) Example: Polyvinylidenedifluoride …-CH2-CF2-CH2-CF2-….. It has several different crystal phases, which can be modified by processing methods. The alpha phase is non-polar The beta phase is polar PVDF can be processed to contain mostly the polar form, by stretching the film to several time its original length PVDF is semicrystalline - Similar to Teflon (-CF2-CF2-) Electrical Properties of Semicrystalline Materials Semicrystalline materials respond to heat, pressure and external fields. They are used as heat and pressure sensors Thin films can be prepared than have a permanent electric filed across them. These are used as non-stick coatings, selective membranes, etc Electropoled films are used by theelectronics industry, ex. speaker membranes Lattices and Closest Packing How do objects naturally arrange themselves? OR Non-closest Closest If a second layer is added how does that effect the arrangements? 11 Lattices and Unit Cells Mathematicians have shown that there are seven basic geometries in which unit cells can be assembled that completely fill 3-D space. These are called the seven crystal systems We will focus only on the cubic and the hexagonal crystal systems as they describe the vast majority of metallic elements. 12 Unit Cells LATTICE: Identical building blocks : unit cells. i) No “gaps” between them in the lattice. ii) All have same orientation in the lattice. iii) Cannot be arranged in a staggered fashion in the lattice. NOT: OR: OR: 13 Lattices and Unit Cells Consider the smallest possible “unit cell” : The smallest unit cell in a lattice is called the primitive unit cell. In general one would have to consider three-dimensions. 14 Closest Packing The marbles adopted a “closest packing” as in most metals. Two kinds: cubic closest packed hexagonal closest packed. The difference arises when a third row is added: 15 Hexagon Closest Packing Orient the lattice so that the layers are more easily seen: A B A Note every second layer are superimposable, as shown in the case of the red layers. 16 Cubic Closest Packing A B C A Every third layer is superimposible. Note that, there is an atom at each corner of the cube And, the center of each face. It is also called face centered cubic (fcc). 17 Cubic Lattices There are three types of cubic unit cells: Note in some cases only parts of an atoms is contained by the unit cell. i.e. The unit cell only contains the fraction of each atom that is *inside* the 18 cube! Lattices and Unit Cells 19 Co-ordination Number, Density and Metallic Radii The number of atoms an atom contacts in the lattice is referred to as its co-ordination number. Determine the coordination number of the following lattices: Simple cubic (e.g. Po) Face-centered cubic (e.g. Cu) Body-centered cubic (e.g. Na) Hexagonal closest packed (e.g. Mg) Lattice type is related to density. What is the relative order of density from most to least dense? How would you measure the density of a metal? How could you relate the lattice type and density to the atomic radius? 20 EXERCISE 1. Aluminum has a density of 2.699 g· cm–3, and the atoms are packed into a face-centered cubic unit cell. Use this information to find the radius of an aluminum atom. Count: there are 4 Al atoms per unit cell by counting rules m 4 26.98 g mol 23 3 V 6.6398 10 cm 23 d 2.699 g cm3 6.022 10 1mol For any cube, a 3 V 3 6.6398 1023 cm3 4.049 108 cm 4.049 1010 m By geometry, face diagonal d 4r 2a r 2 4.049 1010 m 143 pm 4 Along the face diagonal, there are two half and one whole sphere The diagonal length is (a2 + a2)1/2 and corresponds to 4 atomic radii (a a) 2 a 2 a 2 2a 2 a 2 1 EXERCISE 2) Lithium has a metallic radius of 152 pm and the atoms are packed into a body-centered cubic unit cell. Calculate the density of lithium. 22 Cubic Lattices Lattice simple cubic body-centered cubic face-centered cubic Packing fraction 0.5236 0.6802 0.7405 Density (m/r3) 0.125 0.162 0.177 23 Lattices, Density and Metallic Radii Europium has a metallic radius of 198.4 pm and a density of 5.243 g/cm3. Which cubic units cell is the likely for this crystal structure? 24