AS Chemistry Revision Notes Unit 1 Structure, bonding and main group chemistry

Warren Rieutort-Louis Topic 1.3 Structure and Bonding

IONIC Bonding: o In ionic bonding, metal atoms lose electrons and non-metal atoms gain electrons to form ions, which are then held together by strong electrostatic interactions. o An ionic bond involves the transfer of electrons.

o The higher the charge, the smaller the ionic radius. COVALENT Bonding: o In covalent bonding, non-metal atoms share electrons to form molecules; each atom making up the covalent bond has a full outer shell giving it more stability. o A covalent bond involves the sharing of electrons. DATIVE COVALENT Bonding: o In dative covalent bonding, atoms share electrons as in covalent bonding, but both electrons come from one of the bonding species. o Some elements (such as Be, B and Al) bond covalently to form electron deficient compounds. These can then form dative bonds with other compounds to help to get the full octet of electrons. o Electron donor is electron rich o Electron acceptor is electron deficient.

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Charge clouds: o Bonding orbitals are molecular orbitals formed by the bonding of two or more atoms. They can be either sigma or pi bonds. o Sigma: [two s] or [two p] or [one s and one p] orbitals overlap head on o

(two s-orbitals)

(two p-orbitals)

o Pi: two p orbitals overlap sideways. This is weaker than a sigma bond

The intermediate nature of some bonds: o This can be due to 2 things o 1- ELECTRONEGATIVITY DIFFERENCE Electronegativity is the power of an atom to withdraw electron density from a covalent bond. The pair of electrons is therefore unequally shared between the atoms involved in the covalent bond Electronegativity increases across a period and up a group. A difference in Electronegativity between atoms in a covalent bond leads to a polar bond. A polar bond is a covalent bond in which there is a separation of charge between one end and the other. The positive or negative end of a polar bond is called a dipole.

No electronegativity difference between two atoms leads to a pure non-polar covalent bond.

A small electronegativity difference leads to a polar covalent bond

A large electronegativity difference leads to an ionic bond.

o 2-POLARISING POWER OF CATIONS + POLARISABILITY OF ANIONS Not all ionic bonds are completely ionic. The cation (+ve) may pull electrons from the anion (-ve). Factors affecting polarization: Small + highly charged cation: - high charge density Large anion: - outer electrons held weakly. Polar bonds can form both polar and non-polar molecules. o For example, HCl is polar (+ HCl -) and so is CHCl3:

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o However, CCl4 is not polar because the molecule is symmetrical and the dipoles cancel out due to their even spreading. Intermolecular forces act between molecules. o Van der Waals forces are very weak, acting between molecules with dipoles. There are three types: a. Permanent dipole permanent dipole attraction occurs between polar molecules. b. Permanent dipole induced dipole attraction occurs between a polar molecule and a non-polar molecule, whereby the polar molecule induces a dipole on the non-polar molecule. c. Instantaneous dipole induced dipole or dispersion forces attraction occurs between two non-polar molecules, whereby a dipole is instantaneously produced on one; inducing a dipole on the other. o Hydrogen bonding is a dipole dipole attraction between a hydrogen atom with a + charge, and a highly electronegative atom with a lone pair of electrons (N, O or F). It is much stronger than Van der Waals forces, but still weak. o This results in unusually high boiling points in compounds such as H2O and HF.

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The different types of structures: Examples: H2, I2, Cl2, HCl

Made up of small molecules. The bonding within the molecules is strong covalent but weak vd Waals forces exist between the molecules.

Simple Molecular
Very brittle when solid

Low melting and boiling points due to weak intermolecular forces between molecules.

Usually liquids and gases They do not conduct electricity because there are no ions or free electrons.

Hydrogen bonds between molecules are stronger than other intermolecular forces. So water has a higher melting temperature than expected and is a liquid and not a gas.

Examples: H2O, NH3

Hydrogen-bonded molecular

Electrical insulators as there are no charged particles to carry current

Ice has a lower density than water (maximum density at 4oC). Four hydrogen bonds hold each water molecule in place. On melting, they are broken and structure collapses to give a lower volume liquid. Water expands on freezing so ice floats as it has a lower density than water.

High melting points and boiling points and are solids at room temperature because ions are held firmly in place by strong ionic electrostatic forces. Medium Densities Dissolve in water if big enough attractions between water molecules and the ions to Warren Rieutort-Louis 2004 overcome the attractions between the ions themselves. Insoluble in organic solvents.

Do not conduct when solid but do when molten because of free ions

Ionic Structures

Brittle: Ions of the same charge are brought side-by-side and so the crystal repels

NaCl is 6:6 coordinated (i.e. each Na+ has 6 Cl- around it) Caesium Chloride is 8:8 coordinated

Thousands of atoms held together by strong covalent bonds

Giant atomic/molecular

They are insoluble in both polar and non-polar solvents, because the bonds are too strong

High melting and boiling points because it takes a lot of energy to break these bonds

Do not conduct electricity because there are no ions or free electrons

o DIAMOND: Hard High Melting+ Boiling points Insoluble and insulator High density o GRAPHITE: Soft because of large distances between layers High Melting + Boiling points Low Density because of large space. Insoluble Conducts electricity because of free delocalised electrons. The bonding in polymers: o Branched Polymers: Low density.

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Branches prevent the chains from lying close together in a tidy arrangement. Dispersion forces are less and the plastic is weaker Low melting point.

o Unbranched Polymers: High density. Branches close. Large dispersion forces and the plastic strong High melting point. Trends in boiling points of the group 4 hydrides. o Increase in boiling point because molecules are getting larger with more electrons, and so van der Waals dispersion forces are greater.

Trends in boiling points of the group 5,6,7 hydrides. o Trend is generally the same as in group 4 o BUT boiling point of the hydride of the first element is abnormally high. o This is due to the powerful hydrogen bonds., requiring significantly more heat energy to break. State changes: o Melting endothermic o Boiling endothermic o Freezing exothermic o Condensation exothermic Shapes of molecules:

BeCl2 CO2 HCl SO2

linear linear linear bent

2 single bonds 2 double bonds 1 single bond, 3 lone pairs 2 double bonds, 1 lone pair

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H2O

bent

2 single bonds, 2 lone pairs

BCl3

trigonal planar 3 single bonds

NH4+

tetrahedral

3 single bonds, 1 coordinate bond

CH4

tetrahedral

4 single bonds

NH3 SO32-

pyramidal pyramidal

3 single bonds, 1 lone pair 1 double, 2 coordinate, 1 lone pair

SO42-

tetrahedral

2 double, 2 single

CO32-

trigonal planar 2 single bonds, 1 double bond

NO3-

trigonal planar 2 double bonds, 1 single bond

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PCl5

trigonal bipyramidal

5 single bonds

SF6

octahedral

6 single bonds

VSEPR Theory o In a molecule, pairs of electrons called negative centres surround the central atom. o These negative centres repel each other and arrange themselves to be as far apart as possible. o Lone pairs repel more strongly than negative centres therefore they position themselves even further away o Lone pair lone pair repulsion > lone pair bond pair repulsion > bond pair bond pair repulsion. o The shape of a molecule is based on the number of electron pairs that it has: a. 2 pairs linear (180) b. 3 pairs trigonal planar (120) c. 4 pairs tetrahedral (109.5) d. 5 pairs triangle bipyramidal (120 equatorial, 90 axial) e. 6 pairs octahedral (90). o With lone pairs: TETRAHEDRAL Angle becomes 107 (e.g. NH3) (1 lone pair) 2 bond pairs two lone pairs Angle becomes 105

Metallic bonding: o Metallic bonding occurs when metal atoms lose their outer electrons, which form a sea of delocalised electrons, holding together a regular lattice of positive ions. o The bonding is the force of attraction between the delocalised electrons and the positive ions. o High melting points because of strong attraction between electrons + cations o Conduct electricity because of delocalised electrons.

Warren Rieutort-Louis 2004