Topic 1.

6 Bonding

Ionic structures summary

Characteristics of ionic compounds

Hard

Brittle

high m.p.

conduct electricity when molten

do not conduct when solid

soluble in polar (but not in non-polar) solvents

attraction

You should be able to explain all these in terms of inter-particulate forces

repulsion

Ionic radii

determined from x-ray diffraction

( 100pm = 10-10m = 1; ionic radius 100pm)

cation radius < parent atom

anion radius > parent atom

32+
2+
3+

isoelectronic: N > O > F (> Ne) > Na > Mg > Al

i.e. for same number of e , as nuclear charge , radius

Periodic trends: F < Cl < Br < I

i.e. for same effective nuclear charge, as no. of shells , radius
Lattice energy

is the energy change when one mole of an ionic

solid is formed from its ions in the gas phase

May be predicted from electrostatic theory

Small radius and high charge high LE

High co-ordination number high LE

High LE high m.p.

3-d structures

Consider cations in spaces between anions

CN=8 large cation/anion radius ratio (e.g. CsCl)

CN=6 intermediate cation/anion radius ratio (NaCl)

CN=4 small cation/anion radius ratio (e.g. ZnS)

Dissolution

Ionic compounds tend to be soluble in water

2
M + (aq ) + X (aq )
e.g. MX (s )
Driving force is the hydration of ions (dative covalent bonds)
Strong coordination solid hydrates (e.g. MgCl2.6H2O)
Ionic compounds tend to be insoluble in organic solvents

H O

Polarisation (partial covalency) of ionic lattices

Distortion of spherical electron density

Favoured by small highly charged cations (highly polarising)

Favoured by large highly charged anions (highly polarisable)

2+
+

Favoured by cations with incomplete outer shell (e.g. Cu , Ag )

Lattice energy is greater in magnitude (i.e. more negative) than predicted by electrostatic theory

May be insoluble

May have lower m.p. than expected due to formation of molecules in liquid phase (e.g. AlCl3)