Sunway College Johor Bahru Cambridge A-Levels Chemistry

Topic 3: Chemical Bonding

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(a) *describe ionic (electrovalent) bonding, as in sodium chloride and magnesium oxide, including the use of dot-and-cross diagrams (b) *describe, including the use of dot-and-cross diagrams, (i) covalent bonding, as in hydrogen, oxygen, chlorine, hydrogen chloride, carbon dioxide, methane, ethene (ii) co-ordinate (dative covalent) bonding, as in the formation of the ammonium ion and in the Al2Cl6 molecule (c) *explain the shapes of, and bond angles in, molecules by using the qualitative model of electron-pair repulsion (including lone pairs), using as simple examples: BF3 (trigonal), CO2 (linear), CH4 (tetrahedral), NH3 (pyramidal), H2O (non-linear), SF6 (octahedral) (d) *describe covalent bonding in terms of orbital overlap, giving and bonds (e) *explain the shape of, and bond angles in, the ethane, ethene and benzene molecules in terms of and bonds (see also Section 10.1) (f) predict the shapes of, and bond angles in, molecules analogous to those specified in (c) and (e)
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 (g) describe hydrogen bonding, using ammonia and water as simple examples of molecules containing N-H and O-H groups (h) explain the terms bond energy, bond length and bond polarit and use them to compare the reactivities of covalent bonds (i) *describe intermolecular forces (van der Waals forces), based on permanent and induced dipoles, as in CHCl3(l); Br2(l) and the liquid noble gases (j) describe metallic bonding in terms of a lattice of positive ions surrounded by mobile electrons (k) *describe, interpret and/or predict the effect of different types of bonding (ionic bonding, covalent bonding, hydrogen bonding, other intermolecular interactions, metallic bonding) on the physical properties of substances (l) deduce the type of bonding present from given information (m) show understanding of chemical reactions in terms of energy transfers associated with the breaking and making of chemical bonds
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How ions formed and Ionic bonding

Ions are formed when atoms lose or gain electrons Positive ions are formed when an atom loses one or more electrons. Metal atoms usually lose electrons and form positive ions Negative ions are formed when an atom gains one or more electrons. Non-metal atoms usually gain electrons and form negative ions. When metals combine with non-metals, the electrons in the outer shell of the metal atoms are transferred to the non-metal atoms. The strong force of attraction between the oppositely charged positive and negative ions results in an ionic bond or electrovalent bond. In an ionic structure, the ions are arranged in a regular repeating pattern. Ionic bonding is very strong
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Dot-and-cross Diagrams
It shows The outer electron shells only The charge of the ion is spread evenly by using square brackets The charge on each ion, written at the top righthand corner of the square brackets

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Covalent Bonding
When two non-metal atoms combine, they share one or more, pairs of electrons. A shared pair of electrons is called a single covalent bond or a bond pair The pairs of outer-shell electrons not used in bonding are called lone pairs. Each atom in a chlorine molecule has three lone pairs of electrons and shares one bonding pair of electrons.
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When draw the arrangement of electrons in a molecule Use a dot for electrons from one of the atoms and cross for the electrons from the other atom If there are more than two types of atom then can use additional symbols such as a small triangle Draw the outer electrons in pairs, to emphasize the number of bond pairs and number of lone pairs

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 Some cases where the electrons around a central atom may not have a noble gas configuration Only elements of Period 3 and beyond can expand their octet to accommodate more than 8 electrons

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Multiple covalent bonds

Double covalent bond is sharing of two pairs of electrons Triple covalent bond

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Co-ordinate Bonding (Dative Covalent Bonding)

Dative covalent bond is formed when one atom provides both the electrons needed for a covalent bond. A co-ordinate bond is represented by an arrow. The head of the arrow points away from the lone pair which forms the bond.

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At high temperatures aluminium chloride exists as molecules with the formula AlCl3. This molecule is electron deficient, it still needs two electrons to complete the outer shell of the aluminium atom. At lower temperature, two molecules of AlCl 3 combine to form a molecule with the formula Al2Cl6 The AlCl3 molecules are able to combine because lone pairs of electrons on two of the chlorine atoms form co-ordinate bonds with the aluminium atoms.

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Metallic Bonding
In metal, the atoms are packed closely together in a regular arrangement called a lattice. Metal atoms in a lattice tend to lose their outer shell electrons and become positive ions The outer shell electrons are free to move throughout the metal lattice and known as ???? Why metallic bonding is strong? Because the ions are held together by the strong electrostatic attraction between positive charges and the negative charges of the delocalised electrons The strength of metallic bonding increases with: Increasing positive charge on the ions in the metal lattice Decreasing size of metal ions in the lattice Increasing number of mobile electrons per atom
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Metallic bonding and the properties of metal

Why most metals have high melting points and high boiling points? The strong attractive forces between the metal ions and the delocalised electrons. These attractive forces can only be overcome at high temperatures Why metals conduct electricity? When a voltage is applied to a piece of metal, an electric current flows in it because the delocalised electrons are free to move Why metals conduct heat? The conduction of heat is partly due to the movement of the delocalised electrons and partly due to the vibrations passed on from one metal ion to the next

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Sigma () and Pi () Bonds

In the formation of a covalent bond the atomic orbitals overlap so that a combined orbital is formed, containing two electrons which is called as molecular orbital. The greater the overlap, the stronger the bond bonds are formed by the overlap of an s orbital with another s orbital. (H2) Or overlap of an s orbital with a p orbital (CH4) Or end-on overlap of two p orbitals A sigma bond can be rotated without breaking the bond. bonds are formed by the sideways overlap of two orbitals. A bond is weaker than a bond.

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Sigma () Bonds

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Pi () Bonds
bonds are formed by the sideways overlap of two orbitals. A pi bond cannot be rotated without breaking the bond.

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Shapes of molecules
Electron-pair Repulsion Theory All electrons have the same charge so they repel each other when they are close together. A pair of electrons in the bonds surrounding the central atom in a molecule will repel other electron pairs This repulsion forces the pairs of electrons apart until the repulsive forces are minimised Lone pairs of electrons have a more concentrated electron charge cloud than bonding pairs of electrons. Lone pair-lone pair repulsion > lone pair-bond pair repulsion > bond pair-bond pair repulsion The repulsion between electron pairs is increased by the increase in electronegativity of the central atom
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Predict shapes of molecules

Decide which atom at the centre of the molecule Determine the number of electron pairs around the central atom Look up number of valence electrons in central atom Add one electron for each atom joined to central atom Add electron if particle is negatively charged; Subtract electron if particle is positively charged Divide by two to get the number of electron pairs Determine the number of bonds and lone pairs and hence, the shape of the molecules Repulsion between lone pairs and bond pairs determines the bond angle
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No. of electron pairs 2 3

No.of bond pairs No. of lone pairs 2 3 2 0 0 1 0 1 2 0 1 2 0

Shape of molecules Linear Trigonal planar V-shape (bent) Tetrahedral Trigonal pyramidal V-shape (bent) Trigonal bipyramidal Distorted tetrahedron T-shape Octahedral

4 3 2

5 4 3

5
4

1
2

Square pyramidal
Square planar
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109.5 104.5 Trigonal pyramidal 107

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Bond Length and Bond Energy

Double bonds are shorter than single bond because double bonds have a greater quantity of negative charge between the two atomic nuclei. The greater force of attraction between the electrons and the nuclei pulls the atoms closer together resulting in a stronger bond The strength of a bond is measure by its bond energy Bond energy is the energy needed to break one mole of a given bond in a gaseous molecule. Bond strength is the distance between the nuclei of the two atoms joined by a covalent bond Bond strength influence the reactivity of a compound Nitrogen is unreactive because it has a triple bond which require a lot of energy to break the nitrogen atoms apart Oxygen is much more reactive as it needs lower amount of energy to break the oxygen atoms apart. However, bond strength is one of the factor influences the reactivity of a molecule. The polarity of the bond and whether the bond is a sigma or pi bond also affect the chemical reactivity.
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Intermolecular Forces
Van der Waals forces / dispersion forces / dipole-induced dipole forces Permanent dipole-dipole forces Hydrogen bonding

Electronegativity Polarity in molecules

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Electronegativity
Electronegativity is the ability of a particular atom, which is covalently bonded to another atom, to attract the bond pair of electrons towards itself Electronegativity increases across a period from Group I to Group VII Electronegativity decreases down a group

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Polarity in molecules
When the electronegativity values of the two atoms forming a covalent bond are the same, the pair of electrons is equally shared. The covalent bond is non-polar When the covalent bond is formed between the two atoms having different electronegativity values, the more electronegative atom attracts the pair of electrons. This is consider as polar

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 The difference in electronegativity values of the atoms in a covalent bond increases, the bond becomes more polar In molecules containing more than two atoms, have to consider the polarity of each bond and the arrangement of the bonds in the molecule Some molecules contain polar bond but do not have overall polarity because the dipoles cancel each other For example, trichloromethane and tetrachloromethane

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Polarity and Chemical Reactivity

Bond polarity influences chemical reactivity For example, nitrogen and carbon monoxide Nitrogen is a non-polar molecule and is unreactive but carbon dioxide is a polar molecule so it reacts with oxygen and also as reducing agent

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Van der Waals forces

Weak forces of attraction keeping the molecules together at room temperature It exist between the all atoms or molecules How do van der Waals forces arise? The electrons in a molecule can, at any moment, be unevenly distributed so that one side of the molecule is slightly positive and the opposite side is slightly negative. This is called an instantaneous dipole An instantaneous dipole in one molecule can induce another dipole in any neighbouring molecule. The two molecules Will then attract each other

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Van der Waals forces increase with increasing number of electrons in the molecule and increasing number of contact areas (shape) of the molecule Enthalpy change of vaporisation and boiling points of the noble gases can be explained by van der Waals forces Both the enthalpy change of vaporisation and the boiling points of the noble gases increase as the number of electrons increases because the van der Waals forces between the atoms are increased with an increasing number of electrons so more energy is needed to change the liquid into vapour and the boiling point is higher

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Permanent dipole-dipole forces

The forces between two molecules having permanent dipoles are called permanent dipole-dipole forces The attractive force between the partial positive charge on one molecule and the partial negative charge on a neighbouring molecule causes a weak attractive force between the molecules Permanent dipole-dipole forces are often stronger than van der Waals forces

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Hydrogen Bonding
The strongest type of intermolecular force For hydrogen bonding to occur: One molecule have a hydrogen atom covalently bonded to F, O or N A second molecule having a F, O or N atom with an available lone pair of electrons When a hydrogen atom is covalently bonded to a very electronegative atom, the bond is very highly polarised Number of hydrogen bonds formed per molecule depends on the number of hydrogen atoms attached to F, O or N in the molecule and the number of lone pairs present on the F, O or N

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How does hydrogen bonding affect boiling point?

The rise in boiling point from HCl to HI is due to the increasing number of electrons in the halogen atoms as going down the group. The boiling point of HF expected to be loer than HCl but it is much higher because of the stronger intermolecular forces of hydrogen bonding between the HF molecules
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Properties of Water

Enthalpy change of vaporisation and boiling point Water has a higher enthalpy change of vaporisation and boiling point than expected This is due to extensive hydrogen bonding The rise in enthalpy change of vaporisation from H2S to H2Te is due to the increasing number of electrons in the Group VI atoms as go down the group
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 Why water has a high surface tension and high viscosity? Hydrogen bonding reduces the ability of water molecules to slide over each other so the viscosity of water is high The hydrogen bonds in water also exert a significant downward force at the surface of the liquid which causes the surface tension of water to be higher than other liquids Why ice is less dense than water? In ice there is three-dimensional hydrogen-bonded network of water molecules which produces a rigid lattice in which each oxygen atom is surrounded by a tetrahedron of hydrogen atoms. This arrangement allows the water molecules to be slightly further apart than in the liquid so the density of ice is less than that of liquid water

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Bonding and physical properties

Physical state at r.t.p Ionic compounds are solids at r.t.p because there are strong electrostatic forces holding the positive and negative ions together and the ions are arranged regularly in a lattice with the oppositely charged ions close to each other Ionic compounds have high melting points, high boiling points and high enthalpy changes of vaporisation Metals, apart from mercury are solids Most metals have high melting points, high boiling points and high enthalpy changes of vaporisation Covalent compound are usually liquids or gases This is because the forces between the molecules are weak
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 Solubility Most ionic compounds are soluble in water This is because water molecules are polar and they are attracted to the ions on the surface of the ionic solid This attractions are called ion-dipole attractions Metals do not dissolve in water Covalent compounds divided into two groups Non-polar molecules are insoluble in water Small molecules that can form hydrogen bonds with water are generally soluble. Some covalent compound reacts with water rather than dissolving in it

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Electrical Conductivity Why ionic compounds do not conduct electricity at solid state but conduct electricity when molten state? This is because the ions are fixed in the lattice and are not free to move. When molten, an ionic compound conducts electricity because the ions are free to move

Metals conduct electricity both when solid and when molten Covalent compounds do not conduct electricity because do not have free ions to move

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