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Iconic bonding
0.1 nm
Formation of ions
An ion is formed when an atom gains or loses one or more electrons. For example, a
copper atom loses two electrons:
Cu(g) Cu21(g) 1 2e2
to form a copper cation. A chlorine atom gains one electron:
Cl(g) 1 e2 Cl2(g) Watch out!
to form a chloride anion.
The formation of an ion is not the same
A positive ion is called a cation, it is attracted towards the cathode in electrolysis.
as the formation of an ionic bond. Ions
A negative ion is called an anion, it is attracted towards the anode in electrolysis.
are formed as ionic bonds are made,
When ions are formed they tend to have a full outer shell, i.e. eight electrons. but they can also be formed by other
This is called the octet rule. Ions with full outer shells have the same electronic means, e.g. electron bombardment in a
configurations as noble gases (Group 0) for example, a Ca21 ion has the same mass spectrometer.
electronic configuration as argon; they are isoelectronic.
Ionic radius increases down a group Ionic radius increases down a group
cations are smaller than their atoms anions are larger than their atoms
Quick Questions
Worked Example
Calculate the lattice energy for calcium chloride: Ca21(g) 1 2Cl2(g) CaCl2(s).
CaCl2(s)
Using the BornHaber cycle, the lattice energy for CaCl2 is given by:
DH lat [CaCl2(s)] 5 [2(2698) 2 244 21145 2 590 2 178 2 796]kJ mol21
5 22255 kJ mol21
This is very large and indicates the strength of ionic forces of attraction
between ions.
Worked Example
Quick Questions
1 How do you find the enthalpy change for the formation of the Al31(g) ion
from the element?
2 What does the general size of lattice energies tell us about ionic bonding?
The different methods of obtaining the lattice energies for the sodium halides produce
very similar results. But this is not the case for the silver halides their lattice energies
are more exothermic (more negative and more stable) than theory would predict.
Coulombs law assumes that the ions are completely separate and spherical (not
distorted).
Experiment therefore suggests there is a degree of electron sharing, i.e. covalency, in
the silver halides, while the sodium halides show (almost) pure ionic bonding.
This is supported by lower melting temperatures for silver halides than sodium halides.
Polarization of ions
Polarization of an ion is the distortion of its electron cloud away from completely
spherical:
a cation will distort an anion Watch out!
a cation has polarizing power
an anion is polarizable. Cations polarize. Anions are polarized.
(a)
(b)
(c)
1
436 kJ mol
Energy released as the
atoms move together
Cl Cl Cl
Al Al
Attractive and repulsive forces
Cl Cl Cl
balance at this separation Dative covalent bonding in Al2Cl6.
The arrows show the electron
0.074 nm
pairs that have come from
The bond length in a hydrogen molecule is 0.074nm chlorine atoms.
Dative covalent bonds are formed when both the shared electrons come from just
one of the atoms.
For example, aluminium chloride, AlCl3, will form dimers (a combination of two Watch out!
identical molecules) of Al2Cl6. The aluminium atom in aluminium chloride is electron-
deficient (only six electrons in its outer shell) but by forming dative covalent bonds the Covalent bonds and dative covalent
octet rule is fulfilled. bonds are exactly the same once they
have been formed.
Atoms can share more than one pair of electrons and form double or triple covalent
bonds:
a double bond results from two shared electron pairs e.g. in oxygen, O2, O5O
a triple bond results from three shared electron pairs e.g. in nitrogen, N2, N;N.
Worked Example
Quick Questions
Watch out!
Sea of electrons,
Be careful! Use the correct names for
only some forces
of attraction are particles atoms in covalent bonds,
shown but ions in ionic bonds.
The attraction between metal ions and electrons keeps the ions in place
The typical characteristics of metals can be explained using this simple model of
metallic bonding.
Electrical conductivity the delocalized electrons are free to move in the same
direction when an electric field is applied to the metal; the movement of charged
particles is an electric current.
Thermal conductivity the delocalized electrons transmit kinetic energy (heat)
through the metal, from a hot region to a cooler one, by colliding with each other.
High melting temperatures the positive ions are strongly held together by the
attraction of the delocalized electrons; it takes a lot of energy to break the metallic
bonds and allow the particles to move around in the liquid state.
Malleability and ductility metals can be hammered into shape (malleable) or
stretched into wire (ductile) because the layers of positive ions can be forced to slide
across each other while staying surrounded by the sea of delocalized electrons.
1 Draw a dot-and-cross diagram to show the arrangement of electrons in phosphorus trichloride, PCl3. You need only show the outer
electrons. (2)
Examiner tip
First find phosphorus in the Periodic Table. It is in Group 5, therefore has 5 outer electrons. Now draw the 3 chlorine atoms around the central
phosphorus, placing each Cl at three of the four points of the compass, and between each Cl and the P draw a cross representing a chlorine
electron. Complete the chlorine atoms by drawing three pairs of crosses around each one, preferably at three compass points.
Now draw a dot next to each of the crosses between the P and Cl atoms. These represent 3 of the 5 phosphorus
outer electrons. Cl P Cl
Finally place a pair of dots at the fourth compass point, these are the two remaining phosphorus electrons a lone pair.
Cl
Basic answer: Many students can draw the correct number of electrons round each Cl atom. (1) However, they may forget to
show the symbols for each atom.
Excellent answer: To get the second mark, you need to show that there are three shared pairs and one lone pair of electrons round the
P atom. (1)
Answers missing out the pair of non-bonding electrons for P, or showing 8 electrons but not as three shared pairs plus one lone pair, would not
gain credit.
2 Explain why beryllium chloride is covalent but magnesium chloride is ionic. (3)
Examiner tip
This is all about the polarizing power of the Group 2 cations in relation to the chloride anion.
The charges on the beryllium and magnesium ions are the same because they are in the same group. However, the Be21 ion has one fewer
electron shells than the Mg21 ion and is very small.
The answer is:
The chloride ion is moderately polarizable. (1)
The Be 21
ion would therefore be very polarizing and polarize the Cl2 ion to form a covalent bond. (1)
The Mg21 ion is larger and not sufficiently polarizing to form a covalent bond with Cl2. (1)
There is frequent confusion between polarizing power and polarizability. Take care not to get the explanation the wrong way round
e.g. the chloride ion polarizes the Be21 ion is incorrect.
Excellent answer: Keep your answers concise (short) and to the point (accurate) but ensure you answer fully. In the question about
BeCl2 and MgCl2 you have to say something about all three types of ion and the clue is that there are three marks available.
3 Magnesium iodide is a compound of magnesium. The radius of the magnesium ion is 0.072 nm, whereas the radius of the iodide ion is
much larger and is 0.215 nm.
a Describe the effect that the magnesium ion has on an iodide ion next to it in the magnesium iodide lattice. (1)
Examiner tip
The electrons around the iodide ion are drawn towards the magnesium ion/Mg21 polarizes I2 ions. (1)
Take care not to get confused between polarizing power and polarizability. Marks will also be lost if you refer to atoms instead of cations.
you must say the Mg21 ion polarizes, not Mg21 polarizes, or that iodine/I2 is polarized.
b What two quantities must be known about the ions in a compound in order to calculate a theoretical lattice energy? (2)
Examiner tip
c Suggest how the value of the theoretical lattice energy would compare with the experimental value from a BornHaber cycle for
magnesium iodide. Give a reason for your answer. (2)
Examiner tip