Chemical Bonding II

Intermediate bonding between ionic and covalent bonds

In general, the electron distribution around ions is regarded as being spherically symmetrical. However, the cation will attract the outer electrons on the anion, distorting it or polarising it to some extent. This polarisation shifts electron density from the anion towards the cation. If the distortion is sufficient, the bonding electrons may be considered partially shared between the ions, ie. The bond develops some covalent character. The extent to which polarisation of ions occurs depends both upon the polarising power of the cation and the ease with which the anion may be distorted and the factors involved are summarised as follows: CATION High positive charge Small size High charge density Stronger polarising power ANION Large size Valence electrons are less attracted by nucleus and dispersed Easier distortion of the electron cloud (easily polarised)

AlCl3, AlBr3, Al I3 are considered predominantly covalent. Aluminium oxide is ionic. BeCl2, BeBr2, BeI2 are simple covalent molecules.

Intermolecular forces In general, there are 3 types of intermolecular forces in simple covalent molecules: Induced dipole-induced dipole attractions (or temporary dipole-induced dipole attractions)

Permanent dipole-dipole attractions

Hydrogen bonding

The term Van der Waals forces is used to include both dispersion forces and dipole-dipole attractions.

Temporary dipole-induced dipole attractions (dispersion forces) Dispersion forces are intermolecular forces of attraction that result from very weak and instantaneous polarisations of their electron clouds of simple molecular substances. Non-polar molecules eg. N2 and CO2 are held mainly by weak dispersion forces. Strength of induced dipole-induced dipole attractions depends mainly on two factors: Number of electrons eg. Pentane, hexane, hexadecane Shape of molecules (degree of branching) eg. N pentane , 2,2-dimethylpropane

Permanent dipole-dipole attractions Dipole-dipole attractions are intermolecular forces of attraction between oppositely charged poles of polar molecules. Generally, the MORE POLAR the molecule, the stronger is the dipole-dipole attraction, and thus the higher is the boiling point provided there is no great difference in the number of electrons. Eg. HBr is less polar than sulfur dioxide and HBr has a lower boiling point than sulfur dioxide. Dipole-dipole attractions are stronger than the dispersion forces. Eg. ICl has a higher boiling point than bromine liquid. Why?

Hydrogen bonding Hydrogen bonding interactions are electrostatic attractions that arise between molecules that have a H atom bonded to another molecule with a small, highly electronegative atom with lone pairs, usually N, O or F. Explanation: When a hydrogen atom is bonded to a very electronegative atom like F, O or N on another molecule, electron clouds in the covalent bond are drawn extensively towards the electronegative atom. Since hydrogen has no inner electron, the bare proton forms fairly strong dipole-dipole attractions with the electron clouds (lone pair electrons) of another molecule. These relatively strong dipole-dipole attractions are called hydrogen bonding.

Note : Strength of bonds/forces : ionic bonds, covalent bonds, metallic bonds >>> hydrogen bonds > permanent dipole-dipole, dispersion forces

2 important criterion for hydrogen bonding to be present:

H atom is covalently bonded to a small highly electronegative atom eg. N, O or F. Presence of lone pair electrons on the small highly electronegative atom, eg. N, O or F.

Eg. Of hydrogen bonding: HF, H2O and NH3. For polar molecules with hydrogen bonding, boiling point depends on Strength of hydrogen bond Extent of hydrogen bond

Molecules held by hydrogen bonding tend to be more soluble in water. Boiling points of certain molecules:

Intramolecular and intermolecular hydrogen bonding Compare 2-nitrophenol and 4-nitrophenol.

Let us study ethanoic acid.

Structure of water and ice; Properties of water Ic is made up of water molecules held by hydrogen bonding. Low density of ice due to hydrogen bonding which creates an open structure in ice. Ice floats on water has a profound ecological significance. Below 4oC, lakes and rivers begin to freeze downwards; fishes and aquatic life can exist under the ice which insulates it. Question: Methane, ammonia and phosphorus trichloride Mr and boiling point data: Methane Mr Boiling point / K 16 111 Ammonia 17 240 Phosphorus trichloride 137.5 347

Solubility: Like dissolves like. Non-polar molecules in non-polar solvents: generally soluble. Why?

Non-polar molecules in water: generally insoluble in water. Exceptions : AlCl3 It undergoes hydrolysis and is soluble in water.

Polar molecules in water Polar substances that can form hydrogen bonding with water are soluble in water as enough energy is released from the hydrogen bonding formed. This is because the interactions between solute-solvent are comparable in strength to that between solute-solute and solvent-solvent interactions. HCl + H2O H3O+ + Cl-

However, not all polar molecules are soluble in water. Eg. Larger alcohols. Some polar molecules eg. Chloroform ( CHCl 3 ) are insoluble in water.

Recycling of materials: Refer to lecture notes of your college

Metallic Bonding Metallic bonds are formed in a giant metallic substance when: Atoms of a metal lose valence electrons to form positively charged cations Valence electrons are loosely held and delocalised, ie. Free to move within lattice Electrostatic forces of attraction exist between the cations and sea of delocalised electrons in a giant metallic lattice structure. Strength of metallic bond is: o o Proportional to number of valence electrons contributed per atom Inversely proportional to ionic size of cation

Bonding and physical properties The type of bonding and structure in a substance has a considerable influence on the physical properties of the substance. Giant ionic substances Giant ionic lattice structures consist of oppositely charged ions held together by electrostatic forces of attraction. Eg. Sodium chloride They have high melting/boiling points. They are non-conductors of electricity in solid state, but good conductors of electricity in molten or aqueous state. They are generally soluble in water, but insoluble in non-polar solvents (eg. Benzene). Soluble in water: favourable ion-dipole interactions between ions and water molecules are formed and this process releases energy which facilitates the detachment of ions from the ionic lattice for hydration (ie. Solute particles surrounded by water molecules) Insoluble in non-polar solvents : no favourable ion-solvent interactions between ions and non-polar solvent molecules can be formed to break down the giant ionic lattice structure for hydration.

The ionic lattice is hard and brittle. Some of them can be used as refractories: withstand high temperatures due to their high melting points and chemical inertness. Eg. MgO (mp. 2800oC) is used to line the insides of furnaces.

Giant molecular substances Giant molecular structures consist of atoms held together by covalent bonds in a giant extensive network. Eg. Diamond and silicon dioxide They have high melting / boiling points : a large amount of energy is needed to overcome the strong covalent bonds between the atoms in a giant extensive network during melting/boiling. They are non-conductors of electricity in any state: absence of free mobile ions or delocalised electrons to conduct electricity. They are generally insoluble in both water and non-polar solvents: no favourable solute-solvent interactions between solute particles and solvent molecules can be formed to break down the giant molecular structure for hydration/solvation. They are hard. They can be used as abrasives (cutting tools). Giant molecular layered structures consist of atoms held together by covalent bonds in giant extensive flat parallel layers with the adjacent layers held together by Van der Waals forces of attraction. Eg. Graphite They have high melting / boiling points. They are non-conductors of electricity perpendicular to the layers, but good conductors of electricity parallel to the layers. They are generally insoluble in both water and non-polar solvents. They are soft and slippery: adjacent layers are held together by VdW forces of attraction and so the layers can easily slide over one another. They can be used as lubricants.

Simple molecular substances Simple molecular structures consist of molecules held together by either VdW forces of attraction or hydrogen bonds. Eg. Iodine (VdW), Ice (H-bonds)

They have low melting / boiling points : a small amount of energy is needed to overcome either the VdW or H-bonds between molecules during melting/boiling. They are non-conductors of electricity in any state : absence of free mobile ions or delocalised electrons to conduct electricity. They are generally soluble in non-polar solvents, but insoluble in water (exception: acids in water are soluble). They are soft.

Giant metallic substances Giant metallic lattice structures consist of cations in a sea of delocalised electrons held together by electrostatic forces of attraction. Eg. Sodium They have high melting/boiling points. They are good conductors of electricity even in solid state. They are malleable and ductile: a stress applied on a metallic structure causes mere sliding of layers of cations in a sea of delocalised electrons without breaking the metallic bonds; the lattice structure is not shattered. Some of them are used in alloy formation. Metal tensile strength is increased. Recycling of metals are carried out to re-process manufactured products.