Ionic Model and Structures of Solids

M. A. Hayward

Ionic Model Lecture 1:

• Evidence for ions in solids, formulation of the ionic model.

• Lattice energies from thermodynamic cycles.

• Calculated lattice energies: Born-Landé, Born-Mayer and Kapustinskii equations.

• Ionic radii: different definitions and periodic trends.

 Simple Ionic Solids

What holds the atoms in a simple inorganic solid,

like sodium chloride, together in a solid lattice ?

Na A crystal of sodium chloride consists of an ordered regular array of

sodium and chlorine ‘centres’.

We think of them as being ionized as Na+ and Cl- with the attraction
between the unlike charges being responsible for the bonding in the
solid, but is this reasonable ?
Cl
 Evidence for Ions in Solids

Are there really ions in solids ? What evidence is there ?

Electrical Conductivity
If we melt an ‘ionic solid’ or dissolve it in a polar solvent (e.g. water) we get an electrically conducting medium.
This is consistent with the presence ions.

Electronic Spectra
The absorption spectra of ionic solids (e.g. Group 1 metal halides) can be explained on the basis of charge
transfer processes: hν
M+X- MX

There is also a strong similarity between the absorption spectra of gas phase ions and those in solutions and solid
compounds. Best examples are the spectra of compounds containing lanthanide metals.

Magnetic Properties
Magnetic properties of compounds arise from the presence of unpaired electrons. The magnetic properties of
some solid compounds can be rationalised in terms of the behaviour of gas phase ions. Again the compounds of
the lanthanide metals are the best examples. The magnetic behaviour of transition metal compounds can differ
significantly from that of a gas of the corresponding metal ions due to ligand-field effects.

Electron Density Measurements

The electron density in crystal can be determined from high-quality X-ray diffraction data (this is hard to do
accurately). Measurements of this type provide direct evidence of charge transfer in solids and the presence of
anions and cations – see later.
 Definition of the Ionic Model

Ionic Model Assumptions:

• Solids are made up of hard, incompressible, non-polarisable, charged spheres (ions).

• All ions have unit charges (or integer multiples).

• The only interactions between ions are electrostatic.

Force z+ z-

r
Energy

Solid compounds will adopt structures which will maximize unlike ionic interactions (attractions) whilst

minimizing like ion interactions (repulsions). See ALG lectures for details.
 Lattice Enthalpy

Lattice Enthalpy (ΔHL ) of a compound MX is the standard enthalpy change at 298K for the process:

MX M+ + X -

Gas of free ions

Solid lattice (infinite separation between ions)

Sometimes defined as the enthalpy of the reverse process!

For ‘destructive’ definition ΔHLʅ > 0, for ‘constructive’ definition ΔHLʅ < 0

The Lattice Energy (ΔUL) is the corresponding change in internal energy for this process at T = 0 K.
298
ΔHLʅ (298 K) = ΔUL + ∫ [ Cp M+(g) + Cp X-(g) – Cp MX(s) ] dT
0

Where Cp is the heat capacity. ΔHLʅ and ΔUL differ by only a few kJ mol-1 in ~103 kJ mol-1.
 Lattice Enthalpy

Lattice enthalpies cannot be measured directly by experiment. Instead they can be determined from other
experimentally determined enthalpies combined in thermodynamic cycles, such as a Born-Haber cycle.

Na+(g) + Cl-(g)

Electron affinity of chlorine - 368 kJ mol-1

Na+(g) + e- + Cl(g)

Atomisation enthalpy of chlorine + 122 kJ mol-1

Lattice Enthalpy of NaCl
Na+ (g) + e- + 1/
2Cl2(g) + 774 kJ mol-1

1st ionization enthalpy of sodium + 502 kJ mol-1

Na(g) + 1/2Cl2(g)

Atomisation enthalpy of sodium + 107 kJ mol-1

Na(s) + 1/2Cl2(g) NaCl(s)

- 411 kJ mol-1
We can therefore observe that:

ΔHLʅ [NaCl(s)] = ΔHfʅ [Na+(g)] + ΔHfʅ [Cl-(g)] - ΔHfʅ [NaCl(s)]

for the destructive definition.
 Lattice Energy

Can we calculate the lattice energy of a solid ?

z+ z-

r
Coulomb’s Law tells us the energy of interaction between two oppositely charge ions is:

Where charges z+ and z- are the magnitude of the charges separated by distance r, and ε0 is the vacuum permittivity.

In a crystalline solid we need to consider all the interactions between all the ion pairs, with both like and unlike
charges. The number and sign (attractive or repulsive) of these ionic interactions depends of the structure of the
solid. Taking NaCl as an example:

-12 8
A=6 + +
√2 √3

This sum forms a convergent series which depends only on the

structure of the solid, not the chemical identity of the ions, and
is known as the Madelung constant, A.
 Madelung Constant

We can calculate Madelung constant for all regular structures. For example the two mineral forms of ZnS.

4R - 12 ×1.633R + 12 ×1.915R 4R - 12 ×1.633R + 1 ×1.666R + 9 ×1.915R

Blende Wurtzite
A = 1.638 A = 1.641
 Lattice Energy

Thus we can see that the molar lattice energy of a solid with the NaCl structure can be calculated as:

(6 - + ……. )

Where N is Avagadro’s number.

We can extend this to any crystalline solid by replacing the sum with the Madelung constant, A, appropriate to
the crystal structure of the compound, generalising the energy to:

This is a reasonable ‘first approximation’ to the lattice energy of a ionic solid.

But we have left out something important……

 Lattice Energy

We can plot the potential energy of two ions as a function of separation using Coulomb’s law.

V 0

r
This suggests that the most stable configuration for the pair of ions is at separation r = 0.

If this were true all the ions in a crystal would collapse into a point of zero size !

We have forgotten to take the repulsive interaction between ions at small values of r into account.
 Lattice Energy

Born repulsion

Born suggested that the short range

repulsion between ions can expressed as :

V 0
Net potential

UL Where B is a constant and the exponent n

can be determined from compressibility
data (n = 9 for NaCl).
r

This gives a more realistic potential energy curve. We therefore need to include this term in our equation for
the lattice energy:

The value of U changes with r. The equilibrium structure of a solid occurs when U is minimized as a
function of r. We can use differential calculus to determine the value of B at equilibrium. The rearranged
equation becomes:
Born–Landé Equation
 Lattice Energy

If we instead approximate the short range ionic repulsion as : /

we get:
Born–Mayer Equation

Born–Landé Equation Born–Mayer Equation

These two equations allow us to calculate the lattice energy of a solid if we know:

The ionic charges, z + and z –

The inter-nuclear distance, r
The exponents n or ρ (average values are n = 9 and ρ = 34.5 pm)
The Madelung constant, A, for the structure concerned.

But what if we don’t know the structure of the compound ?

 Kapustinskii Equation
Kapustinskii made an interesting observation:

Structure Coordination Madelung Number of ions in A/v

numbers constant (A) formula unit (ν)
NaCl (rock salt) 6:6 1.747 2 0.873

CsCl (caesium chloride) 8:8 1.762 2 0.881

ZnS (blende) 4:4 1.638 2 0.819

ZnS (wurtzite) 4:4 1.641 2 0.820

CaF2 (fluorite) 8:4 2.519 3 0.839

TiO2 (rutile) 6:3 2.408 3 0.802

Al2O3 (corundum) 6:4 4.171 5 0.834

The ratio of Madelung constant, A, to the total number of ions per formula unit, ν, is approximately constant for
compounds which adopt a wide variety of structures.

The value of A/ν varies by less than 10% from the value of 0.87 calculated for NaCl.
 Kapustinskii Equation

If we make the following approximations:

i) Replace A with 0.87ν

ii) Take the inter-nuclear separation, r, as the sum of the ionic radii.
iii) Use the value of n = 9 from the NaCl structure as an average for all structures.

We can substitute into the Born-Landé equation to get the Kapustinskii equation:

. ×
ΔHLʅ (in kJ mol-1)
( )/

Born–Landé Equation Kapustinskii Equation

The Kapustinskii equation allows us predict lattice enthalpies within ~10% of experimental values, for
most compounds. All we need to know are the ionic radii of the ions in the compounds.
 Ionic Radii

The Kapustinskii equation allows us to make good estimates of the lattice energies of solids if we know the radii
of the constituent ions, but what is the radius of an ion ?

Quantum mechanics tells as that the electron distribution of an atom or ion decreases asymptotically with
increasing radius. This isn’t very helpful !

What we can do is measure interatomic distances very accurately, but this just gives us the sum of the radii,
(rA + rB) not the individual radii.

a0

z+ z-

rA + r B
 Ionic Radii

How do we divide up the interatomic distances into separate ionic radii ?

Landé
LiI is a solid with a very large anion and small cation. If we assume that the iodide ions are touching we can then
calculate the ionic radius of I- and hence Li+. By examining the interatomic distances of other solids containing I-
and Li+ we can build up a list of ionic radii.

Pauling
Pauling took a more theoretical approach. He observed that in many-electron atoms and ions, shielding and
penetration were important so we need to consider the effective nuclear charge: Zeff = Z – σ, where Z is the true
nuclear change and σ is the shielding constant, calculated from Slater’s rules.

Pauling proposed that: = =

−

Where Cn is a constant that depends on the principal quantum number n

A pair of isoelectronic ions, such as Na+ and F-, should have the same values of Cn . Thus:
( ) −
=
( ) −

We know the sum r(Na+) + r(F-) from crystallography, so we can now calculate that r(Na+) = 95 pm and r(F-) = 136 pm
 Ionic Radii

Shannon and Prewitt

Shannon and Prewitt took an empirical approach. They complied a list of more than 1000 compounds and evaluated
a set of self-consistent ionic radii which reproduced the observed inter-atomic distances. Cation radii are based on
fixing r(O2-) = 140 pm, r(F-) = 133pm. The values obtained are in pretty good agreement with the other methods of
determining ionic radii. The Shannon and Prewitt radii are the most commonly used data set.

Li+ Be2+ N3- O2- F-

76 45 146 140 133
Na+ Mg2+ Al3+ P3- S2- Cl-
102 72 54 190 184 133
K+ Ca2+ Sc3+ Cu+ Zn2+ Ga3+ As3- Se2- Br-
138 100 75 77 74 62 220 198 196
Rb+ Sr2+ Y3+ Ag+ Cd2+ In3+ Te2- I-
152 118 90 115 95 80 221 220
Cs+ Ba2+ La3+ Au+ Hg2+ Tl3+
167 135 104 137 102 88

These radii are often described as ‘crystal’ radii as they have been derived from a large number of
carefully measured crystal structures.
 Ionic Radii

If we measure the electron density in a crystal using very precise X-ray diffraction measurements we
discover that none of the ionic radii determined by the different methods corresponds to the minimum in
electron density between ions.

The electron density of Li+ isn’t

looking very spherical!
 Trends in Ionic Radii

Ionic radii increasing Li+ Be2+ N3- O2- F-

76 45 146 140 133
Na+ Mg2+ Al3+ P3- S2- Cl-
102 72 54 190 184 133
K+ Ca2+ Sc3+ Cu+ Zn2+ Ga3+ As3- Se2- Br-
138 100 75 77 74 62 220 198 196
Rb+ Sr2+ Y3+ Ag+ Cd2+ In3+ Te2- I-
152 118 90 115 95 80 221 220
Cs+ Ba2+ La3+ Au+ Hg2+ Tl3+
167 135 104 137 102 88

Ionic radii decreasing

• Radii of ions within a group increase with increasing atomic number, Z.

 Trends in Ionic Radii

Ionic radii increasing Li+ Be2+ N3- O2- F-

76 45 146 140 133
Na+ Mg2+ Al3+ P3- S2- Cl-
102 72 54 190 184 133
K+ Ca2+ Sc3+ Cu+ Zn2+ Ga3+ As3- Se2- Br-
138 100 75 77 74 62 220 198 196
Rb+ Sr2+ Y3+ Ag+ Cd2+ In3+ Te2- I-
152 118 90 115 95 80 221 220
Cs+ Ba2+ La3+ Au+ Hg2+ Tl3+
167 135 104 137 102 88

Ionic radii decreasing

• Radii of ions within a group increase with increasing atomic number, Z.

• In a series of isoelectronic cations (e.g. Na+, Mg2+, Al3+) radii decrease with increasing charge.

This makes sense, as the nuclear charge is going up, yet the number of electrons is staying the same, so the
effective nuclear charge Zeff is rising. (Zeff = Z – σ)
 Trends in Ionic Radii

Ionic radii increasing Li+ Be2+ N3- O2- F-

76 45 146 140 133
Na+ Mg2+ Al3+ P3- S2- Cl-
102 72 54 190 184 133
K+ Ca2+ Sc3+ Cu+ Zn2+ Ga3+ As3- Se2- Br-
138 100 75 77 74 62 220 198 196
Rb+ Sr2+ Y3+ Ag+ Cd2+ In3+ Te2- I-
152 118 90 115 95 80 221 220
Cs+ Ba2+ La3+ Au+ Hg2+ Tl3+
167 135 104 137 102 88

Ionic radii decreasing

• Radii of ions within a group increase with increasing atomic number, Z.

• In a series of isoelectronic cations (e.g. Na+, Mg2+, Al3+) radii decrease with increasing charge.
• In a series of isoelectronic anions (e.g. N3-, O2-, F-) the radii decrease with decreasing charge.

In a series of isoelectronic anions, the nuclear charge, Z, declines with increasing ionic charge, thus Zeff
declines with increasing anionic charge, leading to an increase in ionic radii.
 Trends in Ionic Radii

Ionic radii increasing Li+ Be2+ N3- O2- F-

76 45 146 140 133
Na+ Mg2+ Al3+ P3- S2- Cl-
102 72 54 190 184 133
K+ Ca2+ Sc3+ Cu+ Zn2+ Ga3+ As3- Se2- Br-
138 100 75 77 74 62 220 198 196
Rb+ Sr2+ Y3+ Ag+ Cd2+ In3+ Te2- I-
152 118 90 115 95 80 221 220
Cs+ Ba2+ La3+ Au+ Hg2+ Tl3+
167 135 104 137 102 88

Ionic radii decreasing

• Radii of ions within a group increase with increasing atomic number, Z.

• In a series of isoelectronic cations (e.g. Na+, Mg2+, Al3+) radii decrease with increasing charge.
• In a series of isoelectronic anions (e.g. N3-, O2-, F-) the radii decrease with decreasing charge.
• Ionic radii of cations tend to decrease with increasing oxidation state.

Mn2+ Mn3+ Mn4+ Mn5+ Mn6+ Mn7+

66 60 39 33 27 25
Zeff rises with ionic charge in this case (Z constant, σ declines) so cations contract with increasing ionic charge
 Trends in Ionic Radii

Ionic radii increasing Li+ Be2+ N3- O2- F-

76 45 146 140 133
Na+ Mg2+ Al3+ P3- S2- Cl-
102 72 54 190 184 133
K+ Ca2+ Sc3+ Cu+ Zn2+ Ga3+ As3- Se2- Br-
138 100 75 77 74 62 220 198 196
Rb+ Sr2+ Y3+ Ag+ Cd2+ In3+ Te2- I-
152 118 90 115 95 80 221 220
Cs+ Ba2+ La3+ Au+ Hg2+ Tl3+
167 135 104 137 102 88

Ionic radii decreasing

• Radii of ions within a group increase with increasing atomic number, Z.

• In a series of isoelectronic cations (e.g. Na+, Mg2+, Al3+) radii decrease with increasing charge.
• In a series of isoelectronic anions (e.g. N3-, O2-, F-) the radii decrease with decreasing charge.
• Ionic radii of cations tend to decrease with increasing oxidation state.
• Ionic radii of isovalent cations (same charge) tend to decrease on moving from left to right across the
period table – N.B. there are many local variations in the transition metals which will be discussed later
in the course.

As with atomic radii, on moving from left to right across the periodic table, Z increases at a faster rate than σ, so
Zeff rises, leading to a contraction in atomic and ionic radii.
 Ionic Radii

One of the assumptions we made when defining the ionic model is that ions are incompressible. This means that
the radii of ions are ‘fixed’ and should not depend on coordination number.

Cs+
Rb+
K+
The crystal radii determined by Shannon and
Ionic radius (pm)

Prewitt show a strong dependence on coordination

Na+ number.
Ag+
This shows that most ‘ionic’ compounds deviate
from the simple assumptions of the ionic model to
Li+ some degree.

The ions in these solids are not incompressible!

Coordination number
 Thermodynamic Ionic Radii

What is the ionic radius of a non-spherical anion like CO32- ?

r?
r?

CaCO3

Rather than trying to work out which physical dimension represents the ionic radius of carbonate, what we
really want know is the value which we can use in thermodynamic equations to calculate lattice enthalpies.
We call this quantity the Thermodynamic Radius.

We can calculate the thermodynamic radii of species by using Born-Haber cycles to calculate the lattice
enthalpy of a solid containing the ion and then solving the Kapustinskii equation for the size of the anion.
 Thermodynamic Ionic Radii

CaCO3 Ca2+(g) + CO32-(g) ΔHL = 2805 kJ mol-1

We can determine the experimental lattice energy of CaCO3 from thermodynamic cycles.

. ×
ΔHLʅ (in kJ mol-1)
( )/

Using the Kapustinskii equation we can determine the ‘apparent’ sum of the Ca2+ and CO32- ions.

r + + r - = 308 pm

r(Ca2+) = 114 pm, therefore r(CO32-) = 194 pm

This is the thermodynamic radius of CO32-. This value can be used in other thermodynamic calculations
involving CO32- ions.

Now we can use this radius to perform thermodynamic calculations, such as determining the decomposition
temperatures of metal carbonates (see next lecture).
 Thermodynamic Ionic Radii

Using the same process we can determine the thermodynamic radii of other molecular ions.

Ion Thermochemical radius

(pm)
NO3- 130

OH- 140

O2- 149

O22- 159

SO42- 230

N.B. The variation in thermodynamic radii is strongly influenced by covalency as well as the physical ‘size’
of the molecular ions.
 Is the Ionic Model Useful ?

Ionic Model Assumptions:

• Solids are made up of hard, incompressible, non-polarisable, charged spheres (ions).
• All ions have unit charges (or integer multiples).
• The only interactions between ions are electrostatic.

Close inspection of the assumptions of the ionic model show that none of them stand up to scrutiny.

However the ionic model is still pretty good at estimating the lattice enthalpies and other thermodynamic
quantities of simple solids.

This is because it is ‘self correcting’ to a degree – by adjusting the radii of ions we can take account of small
amounts of covalency. In addition by allowing ions to have partial charges we can also get more realistic
behaviour.

The ionic model is useful for a subset of ‘ionic’ solids, but you should be suspicious of results, and aware that
the assumptions we have made are rather simplistic and unrealistic.