Topic 1.

6: Bonding

Summary
Ionic bonding
a) Evidence The existence of ions is shown by the electron density maps of ionic compounds produced by x-ray diffraction. Ionic compounds have high melting and boiling points due to the strong electrostatic forces between particles. They do not conduct electricity in the solid state but do conduct electricity when molten or in solution (when the charged particles are free to move). During electrolysis, positive ions move towards the cathode whilst negative ions move towards the anode. If either or both of the ions are coloured, this motion may be visualised (e.g. copper(II) chromate contains blue cations and yellow anions) as the ions move in opposite directions b) Formation of ions Cations are formed when an atom loses one or more electrons; anions by the gain of one or more electrons c) Dot and cross diagrams + Cations and anions may be represented by dot and cross diagrams showing the net charge on the ions. It is conventional to show the extra electrons on K Cl an anion using the complementary symbol to its own electrons d) Lattices Ionic crystals exist as giant (i.e. infinite) lattices (i.e. regular three-dimensional arrays) of ions e) Ionic bond An ionic bond is the net strong force of attraction between ions in a lattice. The force (F) between two oppositely charged ions is proportional to the magnitude of each charge (q) and inversely proportional to the square of the 2 distance (r) between them: F = k.q1.q2 / r f) Ionic radius The ionic radius is the distance from the centre of the nucleus to the minimum in the electron density distribution between two oppositely charged ions in a crystal. The radius of a given type of ion depends on numerous factors but is roughly constant in a range of environments. Tables of average ionic radii for cations and anions are listed in reference sources. Cations are smaller than their parent atoms whilst anions are larger. Ionic radii increase down a + + + group (e.g. Li < Na < K ) due to the increasing number of electron shells in the ion. Ionic radii for isoelectronic ions 32+ 2+ 3+ decrease with increasing atomic number (e.g. N > O > F > Ne > Na > Mg > Al ) due to the increasing nuclear charge acting on the same number of electrons g) Born-Haber cycle The lattice energy for an ionic compound cannot be determined directly by experiment. It must be determined by applying Hesss Law to the Born-Haber cycle, an example of which is given below for calcium chloride.
2500 Ca2+(g) + 2 Cl(g) 2000 2x Hea, Cl = -710 kJ/mol

1500 Hion, Ca = 1748 kJ/mol

Ca2+(g) + 2 Cl-(g)

H (kJ mol-1)

1000

500 2x Hat, Cl = 242 kJ/mol Hat, Ca = 178 kJ/mol 0

Ca(g) + 2 Cl(g) Hlatt, CaCl2 = -2255 kJ/mol Ca(g) + Cl2(l) Ca(l) + Cl2(l)

Hf, CaCl2 = -796 kJ/mol -500 CaCl2(s) -1000

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h) Calculated lattice energy If the crystal structure of a solid is known from x-ray diffraction it is possible to determine the calculated (or theoretical) lattice energy by applying the equation in (e) and assuming the ionic model (i.e. ions are hard, charged spheres). If this is close to the experimental value determined in (g), the ionic model holds and we can say the solid is ionic. i) Polarisation Polarisation occurs in ionic compounds if the electron density in an anion is distorted by a neighbouring cation j) Factors affecting polarisation The polarising power of a cation decreases with increasing radius and increases with increasing charge The polarisability of an anion increases with increasing radius and increases with increasing charge k) Polarisation and partial covalency Compounds with non-polarising cations and non-polarisable anions (e.g. CsF) fit the ionic model and can be said to be 100% ionic. Compounds with highly polarising cations and highly polarisable anions (e.g. AlP) show a high degree of covalent character and the experimental lattice energy is considerably more negative than the calculated lattice energy l) Predicting formulae of ionic compounds Using a calculated lattice energy in the Born-Haber cycle allows us to estimate a value for the standard enthalpy of -1 formation of hypothetical ionic compounds. In the case of MgCl, this is -121 kJ mol . This suggests that MgCl is thermodynamically stable with respect to its elements so why does it not exist? The answer lies in the fact that MgCl2 -1 is more thermodynamically stable (Hf = -642 kJ mol ) so the enthalpy change for the disproportionation reaction: 2 MgCl Mg + MgCl2 is given by: H = [0 +(-642)] - [2(-121)] = -400 kJ mol and the theoretical MgCl would be predicted to disproportionate into Mg and MgCl2.
-1

Covalent bonding
a) Nature of the covalent bond A covalent bond is a consequence of the increase in electron density in the region between two nuclei due to the sharing of valence shell electrons. This negatively charged region has a strong electrostatic attraction for both positive nuclei, acting as a kind of glue to hold them together. In giant covalent structures (such as diamond) the strong forces which must be overcome in order to separate the atoms lead to a very high melting point and an extremely hard material. Electron density maps (from x-ray or electron diffraction) for molecular structures show a relatively high electron density between bonded atoms and a relative low density between non-bonded atoms. b) Dot-and-cross diagrams Dot-and-cross diagrams of covalent compounds show shared electrons in the overlapping regions between the outer shells of bonded atoms.
+

H
Cl Cl

N H

H
dative bond

single covalent bond

double covalent bond

dative covalent bond

Metallic bonding
a) Structure of metals 2+ 2+ 2+ - 2+ - 2+ 2+ - Metal atoms have only weakly held outer electrons. When in a lattice, one or more 2+ 2+ 2+ 2+ - 2+ 2+ outer electrons are donated from each metal atom into a sea of delocalised electrons leaving a lattice of positively charged ions 2+ 2+ 2+ 2+ - 2+ 2+ - b) Bonding in metals 2+ - 2+ - 2+ 2+ - 2+ 2+ The delocalised electrons are free to move throughout the lattice. At any moment in time, each electron exerts an electrostatic attraction on the positive ions in the lattice thus holding them in place in the lattice. Although the electrons are in a state of constant motion there is always a net attraction to the lattice ions. This non-directional force is known as a metallic bond. c) Properties of metals The positive ions are fixed in a lattice but the electrons are free to move. They carry with them energy and charge. Transfer of energy throughout the lattice results in the conduction of heat, whilst transfer of charge results in the conduction of electricity. If the lattice is distorted by an external force, the ions are still attracted by the delocalised electrons so metals are malleable and ductile. The forces of attraction are strong, resulting in high melting points, especially in metals which can contribute two or more electrons to the sea.

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