Intermolecular forces, Structures and Properties of Materials

van der Waals forces: Occurs between small, non-polar molecules. E.g.between O2, I2, N2, CH4 molecules, etc. This is also called instantaneous dipole-induced dipole Electrons in atoms or molecules move at very high speeds. At any instant in time there may be more electrons one side of the atom or molecule. An instantaneous electric dipole occurs. The region with high concentration of electrons is the negative end of a dipole, and the atomic nucleus is the positive end of the dipole. This instantaneous dipole induces dipole in a neighbouring atom or molecule, which is then attracted. Much weaker than ionic, covalent or metallic bonds. As the size of the molecule increases van der Waals forces increases.

1 Classification of Substances According to Structures

solid

forces of attraction between particles weaken

liquid

Particles (may be molecules, ions or metallic atoms)

gas

} t

forces of attraction between particles broken

forces of attraction between particles weaken

liquid (by raising the temp.) solid (at room temp.)

Gas

forces of attraction between particles broken (by further raising the temp.)

forces of attraction between particles strengthen

liquid solid (at room temp.) (by further lowering the temp.)

gas (at room temp.)

forces of attraction between particles strengthen (by lowering the temp.)

Simple molecular solids

lattice particles: discrete molecules lattice forces: weak intermolecular forces A simple molecular solid consists of a lattice of discrete molecules held together by weak intermolecular forces of attraction such as
1.Van der Waals ( solid I2, S8) 2.Dipole-dipole ( solid SO2, ) 3.Hydrogen bonds ( solid H2O, CH3COOH, Solid NH3 )

1. Low melting points and boiling points: This is because little energy is required to break the weak intermolecular forces. When only Van der Waal's forces are present, the
bigger the molecules the higher the melting and boiling point.

2. Soft and easily distorted Since the intermolecular forces are weak, the molecules can be separated easily 3. Non-conductors of electricity when solid, liquid or aqueous This is because there are no free ions/electrons to carry the current

4 Soluble in non-polar solvents (benzene). Benzenebenzene and iodine-iodine attractions are similar in strength to iodine-benzene attractions. So it is easy for the molecules of nonpolar solvent (such as benzene) to penetrate into the simple molecular solid (such as iodine) and solvate the molecules. 5. Insoluble in polar solvents unless they react with it. Molecules of simple molecular solid (such as iodine) cannot penetrate the polar solvent structure(such as water), because the attraction between water molecules are stronger than either iodine-iodine attractions or iodine-water attractions. Hence simple molecular solids are insoluble in polar solvents. In general, solutes dissolve in solvents to which they are structurally and electrically similar. This is referred to as rule of "like dissolves like". Solubility is likely to be greater if both solute and solvent are polar (or if both are non-polar) than if one is polar and the other non-polar.

Some molecules can dissolve in water: molecules such as ethanol and ammonia form hydrogen bonds with water and dissolve. molecules such as HCl react with the water to form H3O+ and Cl- and dissolve.

Ice is a molecular solid. The lattice forces are hydrogen bonds. The hydrogen and covalent bonds are arranged tetrahedrally around each H2O molecule Because of this tetrahedral arrangement, the H2O molecules are not closely packed together. It contains a lot of empty spaces unlike other crystals When ice melts, the tetrahedral arrangement is lost as the molecules move around. They become more closely packed together. This is why water at 0C is denser than ice and ice floats on top of water When ice melts, the tetrahedral arrangement is broken as the molecules move around. So the molecules come closer together and therefore the liquid is denser than the solid The melting and boiling points of water are relatively low because of the relatively weak hydrogen bonds. But the boiling and melting points are much higher than predicted for molecular solids with similar molecular weights due to hydrogen bonds.

Ionic solids
lattice particles: positive and negative ions lattice forces : strong electrovalent bonds An ionic solid consists of positive and negative ions arranged alternatively in a crystal lattice and are held together by rather strong electrostatic attractions. e.g. Na+Cl- ; Mg2+O2-; (K+)2 SO42-; (AI3+)2(O2-)3.

Sodium chloride (Na+Cl-) Solid NaCI has a giant ionic structure which consists of a lattice of Na+ and Clions held together by strong electrostatic forces of attraction. Each ion is surrounded octahedrally by six oppositely charged ions Since both cation and anion have a coordination number of 6, the structure shows a 6:6 co-ordination.

The geometry of MgO lattice is similar to that of NaCl lattice.

Properties of Ionic Solids:

1 Hard and brittle. Hard because every ion is strongly attracted to the oppositely charged ions around it. Brittle (and can be cleaved) because when the crystal is tapped sharply along a particular plane, it is possible to displace one layer of ions relative to the next. Ions of similar charge then come together and repel each other forcing apart the two portions of the crystal; i.e. the crystal cleaves.
+ + + +

Structure is deformed due to stress +

Repulsion shatters the structure

High melting points and boiling points (non-volatile). This is because a large amount of energy is required to overcome the strong electrostatic forces of attraction in the solid and molten liquid.

3 Good conductors of electricity when molten, but nonconductors when solid. In the molten state, the mobile (or free) ions can conduct electricity. In the solid state, the ions are fixed. 4 Insoluble in non-polar solvents ( CCl4, benzene, hexane) - non-polar solvent molecules are held together by weak intermolecular van der Waals forces. - the ionic interaction in ionic solids is much stronger than the ion-solvent attraction. - therefore the solvent molecules cannot enter the ionic lattice and solvate them

5 Soluble in polar solvents (water, ethanol, propanone) - polar solvent molecules immediately attract ions in the lattice. When the ion-solvent pairing takes place, sufficient energy is released to separate the oppositely charged ions form the lattice.

The solid dissolves forming hydrated ions, Na+(aq) and Cl-(aq)

Metallic Solids
lattice particles: metal atoms (cations) lattice forces : metallic bonds

The structure of metal consists of a giant structure of cationic lattice immersed in a sea of mobile valence electrons. electrons. The electrostatic attraction between the delocalized electron cloud and the metallic ions is the metallic bonding. bonding. The delocalised electrons move randomly throughout the lattice of regularly spaced positive ions.

Metals The metal atoms are closely packed together. Metals are therefore dense. In most metals the atoms are packed closely together , in a close-packed structure In copper, each atom touches 12 other Cu atoms. The coordination number is therefore 12. The larger the coordination number, the denser the solid.

Properties of Metallic Solids :

1 High melting points and boiling points. A large amount of energy is required to break the strong metallic bonds. Melting point increases with the number of outer shell electrons due to greater attractive force between the cations and the electrons.
2 Good conductors of electricity (and heat). Metallic solids conduct electricity as a result of the concerted movement of the mobile/free electrons through the lattice. Metallic solids conduct heat as a result of the exchange of kinetic energybetween the mobile/free electrons in the lattice 3. Strong but malleable and ductile. The delocalised electrons in a metallic solid are highly mobile and so, the atoms can slide over one another without breaking the metallic bonds. The metallic bonds are not directed in space. If a stress is applied to the metal, the structure can change shape

4. Insoluble in both polar and non-polar solvents. The metal-metal attractions are much stronger than either the solvent-solvent attractions or the metal-solvent attractions. Hence, solvent molecules cannot penetrate the metallic lattice and so, cannot solvate it.

Factors Affecting the Strength of Metallic Bonding

1. decreasing size of the metal atom (i.e. the atomic/metallic radius); 2. increasing number of valence electrons of the metal atom.

Metal Sodium Magnesium Aluminium

Number of valence electrons(s) 1 2 3

Melting point (oC) 98 650 660

Metal Lithium Sodium Potassium Rubidium Caesium

Metallic radius (mm) 0.152 0.186 0.231 0.244 0.262

Melting point (oC) 180 98 64 39 29

Giant Molecular solids The lattice particles in giant molecular solids are atoms. All the atoms are held together by strong covalent bonds. Examples of giant molecular structures (or macromolecular solids ) are diamond and silicon The lattice particles in diamond are carbon atoms each carbon atom is joined to 4 other carbon atoms to give a tetrahedral arrangement Diamond has high melting point (} 4000C ). Because a large number of strong covalent bonds have to be broken Diamond is very hard mechanically strong and rigid, due to the strong C-C bonds Does not conduct electricity since it has no delocalised electrons All 4 electrons in the valence shell are localised to form 4 covalent atoms It is insoluble in water

Another allotrope of carbon is graphite Graphite has a layer lattice. Graphite is made up of flat layers of carbon atoms Each carbon atom is bonded covalently to 3 other carbon atoms co-ordination number is 3 The carbon atoms are in six-membered hexagons Three valence electrons from each atom are used to form 3 covalent bonds

The fourth valence electron is delocalised in a giant T bond that extends over the whole layer graphite conducts electricity along the plane of the layers the electrons are able to move throughout the layer and conduct electricity along the layer The carbon-carbon length in graphite is shorter than that in diamond, indicating that the C-C bonds in graphite are stronger The layers are held together by weak Van der Waal's forces Graphite is a poor conductor between layers because electrons cannot move between the layers m.p. of graphite is 3700C because strong covalent bonds must be broken to melt it. They are insoluble in all solvents because of the strong C-C bonds Graphite is slippery because layers can slip over each other They are used as lubricants at high temperature

Ceramics are inorganic, non-metallic compounds which consist of metallic and non-metallic elements bonded together primarily by ionic and/or covalent bonds. e.g. alumina (AI2O)), magnesia (MgO), boron carbide (BC)n, silicon carbide (SiC)n, zirconium oxide (ZrO2), silicon nitride (SiN)n and boron nitride (BN)n. Interatomic bonds are either totally ionic or predominantly ionic but having some covalent character. They include all kinds of earthenware, stoneware and porcelain. In most cases, ,they have been treated at high temperatures (firing) at some stage during manufacture. The great advantage of ceramics is their ability to withstand heat and chemical attack - due to the strong bonding (ionic and/or covalent) present in all ceramics.

Properties of ceramics: 1. High strength Ceramics are strong as steel, light as aluminium and hard as diamond. 2. High thermal stability Ceramics are resistant to heat; they can withstand temperatures of 1300C with no lubrication. 3. chemical inertness Ceramics are resistant to chemical corrosion and they do not rot or rust. , 4. low electrical conductivity Ceramics are good electrical insulators The greatest disadvantage of ceramics is that they are brittle. Unlike metals, ceramics cannot deform to absorb an impact and instead crack. Their atomic bonding prevents the crystalline planes from sliding over .each other.

1. refractory materials for furnace linings, e.g. clay, silica (SiO2), MgO and Al2O3. They have very high melting points and so, can withstand the high temperatures of molten metals, slags and hot gases. They are also resistant to chemical attack. 2. electrical insulators for spark plugs. Al2O3 and MgO (giant ionic solids with high melting points) are used to provide the insulation between electrodes to main.tain a high potential difference. 3. cooking utensils - SiO2 is used in making glass cooking utensils and crockery. 4. biological implants, e.g. elbow and hip joints, knee and tooth implants. Ceramics are used because they are strong, chemical resistant and there is no tissue rejection problem 5. as catalyst supports in auto emission devices which convert harmful gases in engines exhausts to non-pollutants

Metal

Uses 1.making cooking utensils e.g. saucepans and pots.

Properties good thermal conductor. resists corrosion.nontoxic; light. conducts electricity. (electrical conductivity of Al is about 2/3 that of Cu) lighter than Cu. non-toxic. malleable and ductile. light yet strong. (3 times as hard as steel but one-third as heavy) resists corrosion. malleable and ductile. conducts electricity. malleable and ductile.

Aluminium (AI)

2. electrical conductor e.g. Al replacing Cu in overhead cables. 3. for packaging food e.g. kitchen foils.

Duralumin (Al, Cu, Mn, Mg)

1.structural metal e.g. in the construction of aircraft, racing bikes, ships and cars. 1. electrical wires 2. domestic water and gas pipework 3. ornaments, jewellery

Copper (Cu)

Brass (Cu, Zn) Bronze (Cu, Sn)

1.musical instruments 2. ornaments 3.plumbing 4 door handles and beds 1. springs 2. coinage metals 3. spark-resisting tools

stronger and harder than pure Cu. higher tenslIe strength and more readily cast than Cu. enhanced corrosion and wear resistance.

Cupronickel 1 for 'silver' coins (25% Ni) (Cu, Ni)