Bonding & Structure

Ionic Bonding

 Atoms bond to form a full outer shell of electrons or the electron configuration of noble gas.
 Ionic bond is strong electrostatic attraction between oppositely charged ions.
 Ionic bonds form between metals and non-metals.

Properties

 High melting point- many strong ionic bonds must be broken, requires lots of energy.
 Ionic solids do not conduct, because ions in fixed positions and cannot move.
 When molten or dissolved in aqueous solutions, ions free to move to electrodes, hence conduct.
 Brittle- if any layers moved, ions with same charge next to each other, hence repulsion.

Dissolving in Water

 Ionic substances are very soluble in water.

 Water is polar molecule, because oxygen has greater attraction for electrons than hydrogen.
 Therefore, oxygen is more electronegative than hydrogen.

 The positive sodium ion is surrounded by the slightly negatively charged oxygen in H2O.
 The negative chlorine ion is surrounded by the slightly positively charged hydrogen in H2O.
 The ions have become hydrated.

Covalent Bonding

 A covalent bond is a shared pair of electrons.

 Formed between non-metals.
 Involves sharing electron pairs.
 Number of electrons in outer shell is maximum number of covalent bonds that can be formed.
 (Single Bond: 1 shared pair) (Double Bond: 2 shared pairs) (Triple Bond: 3 shared pairs)
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Electron Density Map

 Electron Density: Likelihood of finding an electron at that point in space.

 Lines show electron density around the molecule.
 When atomic orbitals overlap, molecular orbitals form which go around both atoms.
 Equal sharing of electrons means symmetrical electron density map.

Properties of Covalent Substances

 Generally low melting and boiling points, because strong covalent bonds occur only between
atoms within molecules- there is only weak attraction between molecules themselves, which do
not need much energy to break apart.
 Poor conductors of electricity because molecules are neutral- no charged particles to carry current
 Even when dissolved in water, if they remain as molecules, solutions do not conduct electricity due
to no charged particles to carry current.
 Generally, covalent compounds are insoluble or less soluble in water and other polar solvents.

Co-ordinate Bonding

 Coordinate bond forms when both electrons forming the covalent bond come from same atom.
 Also called: dative covalent bonding.
 Represented by an arrow ()- arrow points towards the atom accepting the electron pair.
 Occurs in ammonium ion(NH4+), hydroxonium ion (H3O+)
 We cannot distinguish between covalent and coordinate bonds.

Metallic Bonding

 Bond formed due to the electrostatic attraction of metal cations and sea of delocalised electrons.
 Formed within metals.
 Number of delocalised electrons depends on how many electrons have been lost by each atom.
 Metallic bonding spreads throughout, so metals have giant structures.

Properties

Good conductors of electricity

 Delocalised electrons can move throughout structure.

 An electron from the negative terminal of supply joins the sea of free electrons at one end of the
metal wire while, at the same time, a different electron leaves the wire at the positive terminal.

Strength of Metals
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 Charge- greater charge; stronger attraction between positive ions and electrons.
 Size- smaller the ion, closer ions are to nucleus; stronger electrostatic attraction
 Charge Density- greater the charge and smaller the radius, greater the charge density.
 Metals tend to be strong, because delocalised electrons extend throughout solid, so no individual
bonds to break.

Conduction of Heat

 Good conductors of heat; they have high thermal conductivities.

 Sea of electrons partly responsible; move faster, hence transferring more energy.
 Energy spread by increasingly vigorous vibrations of the closely packed ions.

Malleable and Ductile

 Malleable- can be beaten into shape.

 Ductile- can be drawn into wires.
 After a small distortion, each metal ion still in the exact same environment as before, so new shape
is retained.

Melting Points

 Generally high melting and boiling points because they have giant structures.
 Strong attraction between metal ions and delocalised sea of electrons- hard to separate.

Electronegativity

 The ability of an atom to attract a shared pair of electrons in a covalent bond.

 Pauling scale used as a measure of electronegativity.

Strength depends on three factors:

 Nuclear charge.
 Distance between nucleus and outermost electron.
 Shielding of the nuclear charge by electrons in inner shells.

Trends

 Smaller atom, closer nucleus to the shared outer main level electrons; greater electronegativity.
 Larger nuclear charge for given shielding effect; greater electronegativity.
 As we go up a group, electronegativity increases; atoms get smaller, less shielding.
 As we go across a period, electronegativity increases; nuclear charge increases, atoms get smaller.
 Fluorine is most electronegative; Francium is least electronegative.

Polarity of Covalent Bonds

 About the unequal sharing of electrons between atoms bonded together covalently.
 Property of the bond.

Covalent Bonds between Two SAME Atoms

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 When both atoms are the same, electrons in bond must be shared equally between atoms.
 Both atoms have same electronegativity and bond is completely non-polar.

Covalent Bonds between Two DIFFERENT Atoms

 Electrons in bond not shared equally within atoms.

 Looking at hydrogen fluoride, hydrogen has electronegativity of 2.1, fluorine 4.0.
 Hence electrons in covalent bond attracted towards fluorine.
 Therefore, electron cloud distorted towards fluorine.
 Covalent bonds where one end of molecule is relatively negative and other is relatively positive
are said to be polar.
 Greater difference in electronegativity, more polar the covalent bond.

Forces Acting between Molecules

Three types of intermolecular forces:

 Van der Waals forces- act between all atoms and molecules. Weakest
 Dipole-dipole forces- act only between certain types of molecules.
 Hydrogen bonding- act only between certain types of molecules.
Strongest

Dipole-dipole Forces

 Polarity is the property of a particular bond.

 Molecules with polar bonds may have a dipole moment.
 Dipole moment sums up effect of the polarity of all the bonds in the molecule.
 In molecules with more than one polar bond, effects of each bond may cancel to leave no dipole
moment, or may add up and reinforce each other- depends on shape of molecule.

 Dipole-dipole forces act between molecules that have permanent dipoles.

 In hydrogen chloride, chlorine is more electronegative, hence electrons tend toward chlorine.
 Two molecules which both have dipoles will attract each other.
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 Whatever their starting position, molecules with dipoles will 'flip' to give arrangement where two
molecules attract.

Van der Waals Forces

 All atoms and molecules are made up of positive and negative charges, although neutral overall.
 These charges produce very weak electrostatic attractions between all atoms and molecules.

 At any moment, electrons in an atom could be anywhere, hence distribution of charge changes
every instant.
 Atom will have a dipole at any point in time, even though any particular dipole will exist just for an
instant- temporary dipoles.
 The dipole then affects the electron distribution in nearby atoms, so they are attracted to the
original atom for an instant.
 The original atom has thus induced dipoles in nearby atoms.
 As the electron distribution of the original atom changes, it will induce new dipoles in nearby
atoms, which will be attracted to the original atom.
 These forces are called instantaneous dipole-induced forces or Vanderwaals forces.

Properties

 Act between ALL atoms or molecules at ALL times.

 They exist in addition to any other intermolecular forces.
 Dipole caused by changing position of the electron cloud, therefore more electrons = larger
instantaneous dipole.
 Size of Vanderwaals forces increases with number of electrons present.
 This means that atoms or molecules with larger atomic or molecular masses produce stronger
Vanderwaals forces than atoms of molecules with smaller atomic or molecular masses.

This explains:

 The boiling points of the noble gases increase as atomic number increases.
 The boiling points of hydrocarbons increase as chain length increases.

Hydrogen Bonding
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 Type of intermolecular force with characteristics of dipole-dipole attraction and covalent bonds.
 Considerably stronger than dipole-dipole attraction, weaker than covalent bond.
 Represented as dashes in diagrams
 Linearity always the case with hydrogen bonds, because of electron pair repulsion.
 Requires a very electronegative atom with a lone pair of electrons covalently bonded with
hydrogen.

Required Criteria for Formation

 A hydrogen atom bonded to a very electronegative atom- producing strong partial charges on
the hydrogen atom and the atom it bonds with.
 A very electronegative atom with a lone pair of electrons. These will be attracted to the partially
charged electron deficient hydrogen atom in another molecule to form the bond.

Three Elements that Form Hydrogen Bonds:

 Fluorine
 Oxygen
 Nitrogen

Boiling Points of Hydrides

 Boiling points of H2O, HF and NH3 are all higher than those of hydrides of any other element in
their group- would expect them to be lower if only Vanderwaals forces operating.
 Higher melting point due to hydrogen bonding present in bonding between molecules of these
compounds, and these stronger intermolecular forces make the elements harder to separate.

Structure and Density of Ice

 Hydrogen bonds break and reform easily as molecule move about when water is in its liquid state.
 When water freezes, water molecules no longer free to move about- hydrogen bonds hold
molecules in fixed positions.
 Three dimensional tetrahedral structure formed (like diamond)
 To fit in this structure, molecules slightly less packed than in liquid water, therefore ice is less
dense than water and forms on top of ponds rather than at the bottom.
 This insulates ponds and enables fish to survive through winter.

Living with Hydrogen Bonds

 Proteins are long chain molecules with lots of C=O and N-H groups which form hydrogen bonds.
 These hold protein chain in fixed chains.
 However, relative weakness of hydrogen bonds means shapes of proteins are easily altered.
 Heating proteins above body temperature causes them to lose their shapes, thus their function.
 Explains why enzymes lose their effect when they are heated- we call this protein denatured.

Ironing
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 Iron provides heat to break hydrogen bonds in crumpled material and pressure to force the
molecules into new positions, so that material is flat.
 When iron is removed, the hydrogen bonds reform and hold the molecules in these new
positions, keeping the fabric flat.

DNA

 Deoxyribonucleic acid exists as a double stranded helix.

 Two strands of the spiral held together by hydrogen bonds.
 When cells replicate, hydrogen bonds break (but covalent bonds remain unchanged).
 Two separate helixes then act as templates for a new helix to form on each, so end with copy of
original helix.

Hydrogen bonds in ammonia (Note: linearity)

States of Matter

Solid Liquid Gas

Arrangement of Regular- crystal shapes Random- liquid Random- gas fills its
Particles have straight edges, solids changes shape to fill container.
have definite shapes. bottom of its container.
Spacing Close- solids are not easily Close- liquids are not Far apart- gases are
compressed. easily compressed. easily compressed.
Movement Vibrating about a point Rapid 'jostling' Rapid
Diffusion is very slow Diffusion is slow Diffusion is fast
Solids expand on heating Liquids evaporate Gases exert pressure
Energy Changes on Heating

Heating a Solid

 Upon heating a solid and supplying energy to particles, they vibrate about fixed position.
 Slightly increases the average distance between particles, so solid expands.

Latent Heat of Fusion/ Enthalpy Change of Fusion

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 Energy needed to weaken forces holding particles in solid state.

 When solid melts, temperature doesn't change, because heat energy is absorbed as forces
between particles weakened.

Heating a Liquid

 Energy is supplied to the particles, making them move quicker, hence they have more Ek
 On average, particles move further apart, so liquids expand on heating.

Latent Heat of Vaporisation/ Enthalpy Change of Vaporisation

 Energy needed to break intermolecular forces holding particles in liquid state.

 No temperature change.

Heating a Gas

 Particles gain Ek and move faster.

 Get much further apart, so expand upon heating.

Enthalpy is heat measured under constant pressure.

Temperature depends on average Ek of particles; greater the energy, faster the particles move.

Crystals

 Crystals are solid with a regular shape; particles organised in a regular structure.
 Can be classified by the types of bonding between particles.

Ionic Crystals e.g. NaCl

 Ionic bonding (strong electrostatic attraction between oppositely charged ions)

 (6,6) co-ordinate structure (each Na+ ion surrounded by 6 Cl- ions and vice versa)
 Exists in a giant ionic lattice.
 High melting point- lots of energy required to break strong ionic bonds.
 Conductivity- conducts when molten or dissolved in water.
 Brittle- repulsion occurs if regular arrangement altered.
 Most ionic substances have high solubility in water.

Metallic Crystals e.g. Mg

 Metallic bonding (strong electrostatic attraction between metal

cations and sea of free electrons)
 Metal ions are tightly packed; each ion has 6 nearest neighbours
in the same plane, and 3 above and 3 below the plane, meaning
12 in total.
 High melting point because strong metallic bonds require lots of
energy to break.
 Conductors- conduct when solid or molten as delocalised
electrons move between the ions.
 Malleable and ductile because layers can slide over each other.
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Molecular Crystals e.g. Iodine, I2

 Consist of covalently bonded molecules held together by weak Vanderwaals between molecules.
 Low melting point- weak Vanderwaals forces do not require much energy to break.
 Sublimes from solid to vapour form.
 Non-conductor.
 Soft and breaks easily.
 Not very soluble in water.

Macromolecular Crystals e.g. Diamond

 Strong covalent bonding throughout the whole structure.

 Each C has 4 covalent bonds in a tetrahedral arrangement- bond angle 109.5°.
 Very high melting point (~4000°C)- lots of energy
required to break many strong covalent bonds
 Non-conductor, because no delocalised ions or
electrons.
 Very hard- giant 3D lattice of strong covalent bonds.
 Not soluble in water.

Macromolecular Crystals e.g. Graphite

 Strong covalent bonding in layers and weak Vanderwaals

forces between layers.
 Each C has 3 covalent bonds with other
carbons- bond angle 120°.
 Each C has one electron left in a p orbital which
becomes delocalised within layers.
 Very high melting point (~4000°C)- lots of
energy required to break many strong covalent
bonds
 Conductor, because delocalised electrons
along planes of hexagons can carry charge.
 Soft and layers can slide.
 Not soluble in water.

Covalent Character in 'Ionic' Compounds

 Covalent character increases as:

- Metal ion gets smaller (top of groups).
- Charge on metal ion increases (group 3 > group 2 > group 1)
- Anion gets larger in size ( e.g. I- larger than Cl-)
 Therefore, for example, BeI2 is more covalent than BeCl2, because electron cloud around I- more
easily polarised (bigger cloud and further from nucleus).
 Compounds with high covalent character have similar properties to covalent compounds.
 Bonding & Structure

Shapes of Molecules and Ions

Electron Pair Repulsion Theory

 Each pair of electrons around an atom will repel all the other electron pairs.
 The pairs of electrons will take up positions as far apart as possible to minimise repulsions.
 The electron pairs may be a shared pair (bonded) or a lone pair (non-bonded).
 Lone pair-Lone pair repulsion > Lone pair-Bond pair repulsion > Bond pair-Bond pair repulsion
 Overall charge of compound does not affect shape.

Bonding Pair-Lone Pair Repulsion

 Shared pair of electrons attracted towards nuclei of both atoms in the compound.
 Lone pair only attracted by one atomic nucleus, so pulled closer to it than shared pair.
 Therefore, repulsion between lone pair and bonded pair of electrons is greater than between the
two bonding pairs- pushes the other atoms together, reducing their bond angles.
 General rule: Angle decreases by 2.5° per lone pair

# of lone pair electrons on # of bonding groups (pair electrons) on

Electron-pair Molecular Bond
'central' atom 'central' atom
Geometry Geometry Angle
0 2 linear linear 180
0 3 trigonal planar trigonal planar 120
1 2 trigonal planar bent 117.5
0 4 tetrahedral tetrahedral 109.5
triangular
1 3 tetrahedral 107
pyramid
2 2 tetrahedral angular 104.5
trigonal 90, 120 and
0 5 trigonal bipyramid
bipyramid 180
90, 120 and
1 4 trigonal bipyramid seesaw
180
2 3 trigonal bipyramid T-shaped 90 and 180
3 2 trigonal bipyramid linear 180
0 6 octahedral octahedral 90 and 180
1 5 octahedral square pyramidal 90

2 4 octahedral square planar 90 and 180

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