Ionic Model and Structures of Solids

M. A. Hayward

Ionic Model Lecture 2:

• Thermochemical radii as a means of accounting for small amounts of covalency

• Stability of metal hydrides

• Stability of metal carbonates

• Stability of different metal-oxygen compounds

 Thermochemical Radii
Silver halides (AgF, AgCl, AgBr, etc.) are observed to have a large amount of covalency in their bonding.
We can demonstrate this by looking at thermodynamic cycles and comparing them to ionic model predictions.

Ag+(g) + Cl-(g)

- 368 kJ mol-1

Ag+(g) + e- + Cl(g)
554pm
+ 122 kJ mol-1
ΔHL (AgCl) AgCl adopts the rocksalt structure. Diffraction
Ag+ + e- + 1/ + 897 kJ mol-1 measurements reveal the lattice parameter is
(g) 2Cl2(g)
554pm, thus r(Ag+) + r(Cl-) = 277pm.
+ 730 kJ mol-1
. ×
Ag(g) + 1/
2Cl2(g)
ΔHL (in kJ mol-1)
( )/
We can calculate the lattice enthalpy of AgCl
+ 286 kJ mol-1
using the Kapustinskii equation.
Ag(s) + 1/2Cl2(g) AgCl(s) . × ×
- 127 kJ mol-1 ΔHL = 779.7 kJ mol-1

The calculated and experimental lattice enthalpies do not match.

This is due to interactions outside the ionic model: covalency
 Thermochemical Radii
We can account for this ‘extra’ bonding interaction by adjusting the radii of the ions.
Rather than using crystallographic radii, we can use ‘Thermochemical radii’

The experimentally determined lattice enthalpy of AgCl = 897 kJ mol-1

. × ×
ΔHL = 897 kJ mol-1
( )/

We can use the Kapustinskii equation to work out what the sum of the radii would need to be calculate
the correct lattice enthalpy.

=> r(Ag+) + r(Cl-) = 240 pm

This is the sum of the thermochemical radii of Ag+ and Cl-

 Thermochemical Radii

Crystallographic measurements of AgCl indicate Ionic Model calculations for AgCl indicate

r+ + r - = 277 pm r+ + r - = 240 pm

If we set r(Cl-) =188 pm we get r(Ag+) = 89 pm If we set r(Cl-) =188 pm we get r(Ag+) = 52 pm

r+ / r - = 0.473 r+ / r - = 0.276

Radius ratio rules suggest AgCl should adopt the Radius ratio rules suggest AgCl should adopt a
rocksalt structure according to these radii. structure with 4-fold coordination (blend or
wurtzite) according to these radii.

We need to be careful choosing which set of radii to use!

Crystallographic radii for considering structures (e.g. Shannon and Prewitt radii)

Thermodynamic radii for calculating lattice enthalpies.

 Simple Ionic Solids

We can use the simple thermodynamics of the ionic model to understand trends in the behaviour of simple
inorganic solids.

Group 1 Hydrides
Group 1 metals (Li, Na, K, etc.) react with hydrogen gas to form ‘ionic’ hydrides:

M(s) + ½ H2(g) M+H-(s)

The hydride forming reaction is a reversible equilibrium: Heating the system up leads to a decomposition of
the metal hydrides, back to the elements.

Hydride Tdecomp (°C) We observe that the decomposition temperature of the

group 1 metal hydrides (defined as the temperature at
LiH 550 which the partial pressure of hydrogen = 10 Torr) declines
as we descend the group.
KH 210

CsH 170 Can we explain this ?

If we re-write the equilibrium to focus on decomposition:

M+H-(s) M(s) + ½ H2(g)

We can analyse the equilibrium using the Gibbs free energy relation:

ΔG = ΔH – TΔS

We know that ΔS of the decomposition will be positive (gases have a much higher entropy than solids).
We know that ΔHf of MH will be negative (MH is more enthalpically stable than the elements)

If ΔHf (MH) < TΔS then ΔG < 0 and decomposition will proceed.

If ΔHf (MH) > TΔS then ΔG > 0 for the decomposition and the hydride will be stable.

We can crudely approximate the decomposition temperature to be the point where:

ΔG = ΔH – TΔS = 0

T = ΔH /ΔS
 Stability of Metal Hydrides
Lets consider the equilibrium for lithium hydride:

Li+(g) + H-(g)

-78 kJ mol-1
Li+(g) + e- + H(g)
ΔHL of LiH
+218 kJ mol-1
-915 kJ mol-1
Li+(g) + e- + ½ H2(g)

+520 kJ mol-1
Li(g) + ½ H2(g)

+159 kJ mol-1
Li(s) + ½ H2(g) LiH(s)
-96 kJ mol-1
ΔS = - 65.3 J K-1 mol-1

. × ΔG = ΔH – TΔS = 0
ΔHL (in kJ mol-1)
( )/ For decomposition:
0 = 96,000 – T(65.3)
r(Li+) = 74pm ; r(H-) = 160pm ⇒ T = 1474 K

ΔHL (LiH) = 915 kJ mol-1 N.B. This does not match the previously stated value (823K)
because the value we have calculated is the temperature at
which the equilibrium constant is 1, not the temperature at
which the H2 pressure is 10 Torr.
 Stability of Metal Hydrides

K+(g) + H-(g) Li+(g) + H-(g)

-78 kJ mol-1 -78 kJ mol-1

K+(g) + e- + H(g) Li+(g) + e- + H(g)

ΔHL of KH +218 kJ mol-1 +218 kJ mol-1 -977 kJ mol-1

-724 kJ mol-1 K+(g) + e- + ½ H2(g) Li+(g) + e- + ½ H2(g)

+419 kJ mol-1 +520 kJ mol-1

K(g) + ½ H2(g) Li(g) + ½ H2(g)

+89 kJ mol-1 +159 kJ mol-1

KH K(s) + ½ H2(g) Li(s) + ½ H2(g) LiH(s)
-76 kJ mol-1 -158 kJ mol-1
ΔS = - 65.3 J K-1 mol-1 ΔS = - 65.3 J K-1 mol-1
Tdecomp = 1176 K Tdecomp = 2420 K

. ×
ΔHL (in kJ mol-1)
( )/ The ionic model predicts that KH will decompose at
a lower temperature than LiH.
r(K+) = 138 pm ; r(H-) = 160 pm

ΔHL (KH) = 724 kJ mol-1

 Stability of Metal Hydrides
The more endothermic ΔHdecomp., the more stable the metal hydride and the higher the decomposition temperature.

ΔHatom (M(s)) 1st I.E. (M(g)) Ionic radius ΔHL (MH(s)) ΔHdecomp. Tdecomp.
(kJ mol-1) (kJ mol-1) (pm) (kJ mol-1) (kJ mol-1) (K)

Li 159 520 76 915 96 1474

Na 107 496 102 824 81 1246

K 89 419 138 724 76 1176

Rb 81 403 152 692 68 1046

Cs 96 376 167 660 48 743

ΔHdecomp. = ΔHL(MH(s)) - ΔHatom(M(s)) - I.E.(M(g)) - ΔHatom(H2) - EA(H)

Large ΔHL Small ΔHatom(M) Low I.E.
favours hydride favours hydride favours hydride The same for all hydrides
stability stability stability

The lattice enthalpy of MH dominates ΔHdecomp. so stability of hydrides decreases down the group.
 Stability of Metal Hydrides

What about Group II hydrides ?

Ca2+ has an ionic radius (100pm) which is almost identical to Na+.

Would we expect CaH2 to be more or less stable that NaH ?

. ×
Ca2+(g) + 2H-(g) ΔHL (in kJ mol-1)
( )/
-156 kJ mol-1
r(Ca2+) = 100 pm ; r(H-) = 160 pm
Ca2+(g) + 2e- + 2H(g)
ΔHL(CaH2) = 2492 kJ mol-1
+436 kJ mol-1 ΔHL of CaH2
-2492 kJ mol-1
Ca2+(g) + 2e- + H2(g)
The ionic model predicts that CaH2 should
+1735 kJ mol-1 have a higher decomposition temperature than
NaH:
Ca(g) + H2(g)
NaH Tdecomp = 1246K
+178 kJ mol-1
CaH2 Tdecomp = 2289K
Ca(s) + H2(g) CaH2(s)
-299 kJ mol-1
Experimentally we observe the temperatures
ΔS = - 130.6 J K-1 mol-1 required for 10 Torr H2 are:
Tdecomp = 2289 K NaH ~ 500K
CaH2 ~ 1125K
 Stability of Metal Carbonates

Group II metal carbonates decompose to the corresponding oxides on heating.

MCO3 MO + CO2

How does the stability of Group II carbonates vary down the group ?

Again we have the competition between the enthalpy and entropy, but the situation is more complex because we
have to consider the enthalpies of the carbonate, the oxide and the formation of CO2

If we consider CaCO3 as a specific example, we can construct a thermodynamic cycle for the decomposition:

Ca2+(g) + O2-(g) + CO2(g)

ΔH (1)
-ΔHL (CaO)
Ca2+(g) + CO32-(g)

ΔHL (CaCO3)

CaCO3(s) CaO(s) + CO2(g)

ΔH (2)

ΔH (1) = ΔHf (O2-) + ΔHf (CO2) - ΔHf (CO32-) = 1202 kJ mol-1

 Stability of Metal Carbonates

Ca2+(g) + O2-(g) + CO2(g)

ΔH (1)
-ΔHL (CaO)
Ca2+(g) + CO32-(g)

ΔHL (CaCO3)

CaCO3(s) CaO(s) + CO2(g)

ΔH (2)

We can calculate the lattice enthalpies of CaCO3 and CaO from the thermodynamic radii:

. ×
ΔHL (in kJ mol-1)
( )/

r(Ca2+) = 100 pm, r(CO32-) = 194pm r(Ca2+) = 100 pm, r(O2-) = 140 pm
ΔHL (CaCO3) = 2938 kJ mol-1 ΔHL (CaO) = 3600 kJ mol-1

In addition we can see that ΔH (1) is given by:

ΔH (1) = ΔHf (O2-) + ΔHf (CO2) - ΔHf (CO32-) = 1202 kJ mol-1

 Stability of Metal Carbonates
Ca2+(g) + O2-(g) + CO2(g)

+1202 kJ mol-1
-ΔHL (CaO)
Ca2+ (g) + CO3 2-
(g) -3600 kJ mol-1

ΔHL (CaCO3)
2938 kJ mol-1

CaCO3(s) CaO(s) + CO2(g)

ΔHdecomp. = +540 kJ mol-1

We can therefore work out that ΔHdecomp. = +540 kJ mol-1

The entropy of formation of CO2 = 205 J K-1 mol-1,

so we can determine the decomposition temperature, Tdecomp.

ΔG = ΔH – TΔS = 0

Tdecomp = ΔHdecomp./ ΔSdecomp. = +540 kJ mol-1 / 205 J K-1 mol-1 = 2634K

 Stability of Metal Carbonates
M2+(g) + O2-(g) + CO2(g)

1202 kJ mol-1
-ΔHL (MO)
M2+ (g) + CO3 2-
(g)

ΔHL (MCO3)

MCO3(s) MO(s) + CO2(g)

ΔH (2)

Thinking about the situation more broadly, we can see that the enthalpy of decomposition, ΔH(2), is principally
the difference between the lattice enthalpies of the carbonate and the oxide.

ΔH(2) = ΔHL (MCO3) – ΔHL(MO) + 1202 kJ mol-1

1.08 × 10 × 8 1.08 × 10 × 8
ΔHL (MCO3) = ΔHL (MO) =
( )+ ( ) ( )+ ( )

r (CO32-) > r (O2-), so ΔHL(MO) > ΔHL(MCO3)

As long as this difference is less that 1202 kJ mol-1 the decomposition will be
endothermic and the carbonate will be stable at low temperature.
 Stability of Metal Carbonates

Will the decomposition temperature of MCO3 increase or decease as the radius of M2+ increases ?

The entropy change in the decomposition is constant as the same amount of CO2 is being released each time, so
the decomposition temperature will depend linearly on the enthalpy of decomposition, Δhdecomp.

We know that: ΔHdecomp = ΔHL (MCO3) – ΔHL(MO) + 1202 kJ mol-1

1.08 × 10 × 8 1.08 × 10 × 8
ΔHdecomp = ̶ + 1202 kJ mol-1
( )+ ( ) ( )+ ( )

Substituting in the ionic radii of CO32- and O2- ad rearranging we get:

1 1
Δ Hdecomp = 8.64×105 × [( ) + 194
−
( ) + 140
] + 1202 kJ mol-1

The difference in the lattice enthalpies increases as r(M2+) decreases.

Δ Hdecomp is minimum when r(M2+) = 0

We therefore predict that the decomposition temperature of MCO3 will increase as

r(M2+) increases.
 Stability of Metal Carbonates

The decomposition temperature of Group II metal

ΔHL (kJ mol-1)

MO Mg carbonates increases with cation radius.

Ca
Sr
Ba It is often stated that “large cations stabilize large anions”.
MCO3
But data show that it is more accurate to think that

“small cations destabilize large anions”

Ionic radius (pm)

Radius ΔHL ΔHL ΔHdecomp(MCO3) Tdecomp
(pm) (MCO3) (MO) (kJ mol-1) (K)
(kJ mol-1) (kJ mol-1)
ΔHdecomp(MCO3) = Mg 72 3284 4075 411 2004

ΔHL (MCO3) – ΔHL(MO) + 1202 kJ mol-1 Ca 100 2938 3600 540 2637

Sr 118 2769 3348 622 3036

Ba 135 2626 3141 686 3347

 Stability of Metal Carbonates

What about Group I carbonates ?

Radius ΔHL ΔHL ΔHdecomp(M2CO3) Tdecomp
(pm) (M2CO3) (M2O) (kJ mol-1) (K)
(kJ mol-1) (kJ mol-1)
Li 76 2400 3000 600 2936 The stability of the Group I carbonates
Na 102 2189 2677 713 3480 follows the same trend.

K 138 1951 2330 822 4014 The smaller cations have lower
decomposition temperatures.
Rb 152 1873 2219 855 4173

Cs 167 1795 2110 886 4323

Radius ΔHL ΔHL ΔHdecomp(MCO3) Tdecomp

(pm) (MCO3) (MO) (kJ mol-1) (K)
(kJ mol-1) (kJ mol-1)
We can also observe that the di-valent
Mg 72 3284 4075 411 2004 Group II cations ‘destablize’ the
carbonate anions more, as they have
Ca 100 2938 3600 540 2637 lower decomposition temperatures than
Sr 118 2769 3348 622 3036 the Group I cations with similar radii.

Ba 135 2626 3141 686 3347

 Stability of Metal Carbonates

We can see the influence of cation charge on the stability of carbonates by looking at aluminium carbonate.

2 Al3+(g) + 3 O2-(g) + 3CO2(g)

3 × (1202 kJ mol-1)
-ΔHL (Al2O3)
2 Al3+ (g) + 3 CO3 2-
(g) -16701 kJ mol-1

ΔHL (Al2(CO3)3)
13064 kJ mol-1

Al2(CO3)3(s) Al2O3(s) + 3 CO2(g)

-31 kJ mol-1

r(Al3+) = 54 pm, r(CO32-) = 194pm r(Al3+) = 54 pm, r(O2-) = 140 pm

ΔHL (Al2(CO3)3) = 13064 kJ mol-1 ΔHL (Al2O3) = 16701 kJ mol-1

The decomposition of Al2(CO3)3 is spontaneous at all temperatures – i.e. Al2(CO3)3 is not thermodynamically
stable with respect to Al2O3 and CO2.
 Stability of Metal Carbonates
Radius ΔHL ΔHL ΔHf (M2O) Tdecomp ΔHf (MO)-ΔHf (MCO3)
(pm) (M2CO3) (M2O) -ΔHf (M2CO3) (K) (kJ mol-1)
(kJ mol-1) (kJ mol-1) (kJ mol-1) Experimental
Li 76 2400 3000 600 2936 620

Na 102 2189 2677 713 3480 715

K 138 1951 2330 822 4014 785

Rb 152 1873 2219 855 4173 798

Cs 167 1795 2110 886 4323 -

Radius ΔHL (MCO3) ΔHL (MO) ΔHf (MO) Tdecomp ΔHf (MO)-ΔHf (MCO3)
(pm) (kJ mol-1) (kJ mol-1) -ΔHf (MCO3) (K) (kJ mol-1)
(kJ mol-1) Experimental
Mg 72 3284 4075 411 2004 510

Ca 100 2938 3600 540 2637 572

Sr 118 2769 3348 622 3036 628

Ba 135 2626 3141 686 3347 664

Comparison of our calculated values with experimentally determined values, shows they aren’t bad!
 Group 1 Oxides
When heated in air the Group 1 metals form different oxides

Li+ + O2-
Li + O2 Li2O

Lithium oxide

Na + O2 Na2O2 Na+ + O22-

Sodium peroxide

K + O2 KO2
K+ + O2-

Potassium superoxide
 Group 1 Oxides

Radius (pm) ΔHatom + 1st IE . ×

(kJ mol-1) ΔHL (in kJ mol-1)
( )/
Li 76 679
r(O2-) = 149 pm
Na 102 603

K 138 508

Rb 152 484

Cs 167 472

ΔHL (MO2) ΔHf (MO2)

(kJ mol-1) (kJ mol-1)
ΔHL (MO2)
M+(g) + O2-(g) Li -960 -386

- 105 kJ mol-1 Na -860 -362

M+(g) + e- + O2(g) K -752 -349

ΔHatom + 1st IE Rb -717 -338

M(s) + O2(g) MO2 Cs -683 -316

ΔHf (MO2)

Formation enthalpy of all Group 1 superoxides is exothermic.

 Group 1 Oxides
ΔHL (M2O2)
2M+(g) + O22-(g) ΔHL (M2O2) ΔHf (M2O2)
(kJ mol-1) (kJ mol-1)
+ 625 kJ mol-1
Li -2748 -870
2M+(g) + e- + O2-(g)
Na -2475 -749
- 105 kJ mol-1
K -2175 -639
2M+(g) + 2e- + O2(g)
Rb -2077 -589
2 × (ΔHatom + 1st IE)
Cs -1981 -517
2M(s) + O2(g) M2O2
r(O22-) = 159 pm
2M+(g) + O2-(g)

+ 760 kJ mol-1 ΔHL (M2O) ΔHf (M2O)

(kJ mol-1) (kJ mol-1)
2M+(g) + ½ O22-(g)
Li -3295 -917
ΔHL (M2O)
½ × (+ 625 kJ mol-1 )
Na -2909 -683
2M+ (g) + e- -
+ ½ O2 (g)
K -2503 -467
½ × (- 105) kJ mol-1)
Rb -2375 -387
2M+(g) + 2e- + ½ O2(g)
Cs -2250 -286
2 × (ΔHatom + 1st IE)
r(O2-) = 120 pm
2M(s) + ½O2(g) M 2O
 Group 1 Oxides

The previous analysis shows that the oxides, peroxides and superoxides of all Group I metals all have exothermic
formation enthalpies – they are all more stable than the elements.

Which is the most stable of the three possible oxygen compounds for each metal ?

If we scale the formation enthalpies per mole of metal cations, we can see which is the most thermodynamically
stable oxide, when the metals are burned in excess oxygen.

ΔHf (MO2) ΔHf (M2O2) ΔHf (M2O)

(kJ per mol of M) (kJ per mol of M) (kJ per mol of M)
Li -386 -435 -459

Na -362 -375 -342

K -349 -320 -234

Rb -338 -295 -194

Cs -316 -259 -143

 Group 1 Oxides

Why do we get this trend ?

Radius (pm) ΔHf The lattice energy of solids declines as

(kJ mol-1) ionic radii increase.
Li 76 The ΔHf of oxygen anions becomes
O2 0
increasingly endothermic from O2- to
Na 102
O2- -105 O22- to O2-. Thus we observe the large
K 138 metal cations only generate enough
O22- +520 lattice energy to form superoxide (O2-),
Rb 152 while sodium is small enough to
O2- +1020 stabilize peroxide (O22-) and only
Cs 167 lithium can stabilize oxide ions (O2-)
under these conditions (1atm O2).
 Group 1 Oxides

We can also compare the stabilities of Group I oxides by considering their decomposition reactions.

On heating, superoxides decompose to peroxides and oxygen:

2M+ + O22- + O2
ΔHf (O22-)
– 2 ΔHf (O2-)
- ΔHL (M2O2)
2M+ + 2O2-

2ΔHL (MO2)
ΔHdecomp = -2 ΔHL (MO2) + ΔHf (O22-) – 2 ΔHf (O2-) + ΔHL (M2O2)
2MO2 M2O2 + O2
ΔS = +205 J K-1 mol-1 ΔHdecomp

Radius ΔHL ΔHL ΔHdecomp Tdecomp

(pm) (MO2) (M2O2) (kJ mol-1) (K)
(kJ mol-1) (kJ mol-1)
Li 76 -960 -2748 -98 -
This shows that LiO2 and NaO2 are
Na 102 -860 -2475 -25 - not thermodynamically stable under
1 atmosphere oxygen pressure.
K 138 -752 -2175 +59 287

Rb 152 -717 -2077 +87 424

Cs 167 -683 -1981 +115 560

 Group 1 Oxides

On further heating peroxides decompose in to the corresponding oxides and oxygen.

2M+ + O2- + ½ O2
ΔHf (O2-)
– ΔHf (O22-)
- ΔHL (M2O)
2M+ + O22-

ΔHL (M2O2)
ΔHdecomp = - ΔHL (M2O2) + ΔHf (O2-) – ΔHf (O22-) + ΔHL (M2O2)
M2O2 M2O + ½O2
ΔS = +102.5 J K-1 mol-1 ΔHdecomp

Radius ΔHL ΔHL ΔHdecomp Tdecomp

(pm) (M2O2) (M2O) (kJ mol-1) (K)
(kJ mol-1) (kJ mol-1)
Li 76 -2748 -3295 -47 - Again we can observe that Li2O2 is not
thermodynamically stable under 1
Na 102 -2475 -2909 +66 643 atmosphere of oxygen.
K 138 -2175 -2503 +172 1678

Rb 152 -2077 -2375 +202 1970

Cs 167 -1981 -2250 +231 2253

 Group 1 Oxides
When heated in air the Group 1 metals form different oxides

Li+ + O2-
Li + O2 Li2O

Lithium oxide

Na + O2 Na2O2 Na+ + O22-

Sodium peroxide

K + O2 KO2
K+ + O2-

Potassium superoxide
 Past Paper Question

Inorganic Chemistry
Prelims June 2014:
 Past Paper Question

a) Explain what is meant by the “lattice enthalpy” of an ionic solid. How may the lattice enthalpy of NaCl be
determined experimentally ? [5]
The lattice enthalpy of an ionic solid, MX, is the enthalpy change for the process:

MX(s) M+(g) + X-(g)

Lattice enthalpies cannot be measured directly, but can be calculated from thermodynamic cycles where al
the other terms are known.
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
Past Paper Question
 Past Paper Question

Li+(g) + H-(g)

-78 kJ mol-1
Li+(g) + e- + H(g)
ΔHL of RbH
+436/2 kJ mol-1
-732 kJ mol-1
Rb+(g) + e- + ½ H2(g)

+403 kJ mol-1
Rb(g) + ½ H2(g)

+81 kJ mol-1
Rb(s) + ½ H2(g) RbH(s)
-108 kJ mol-1

. × ×
ΔHL (RbH) = 732 kJ mol-1
( )/ ΔHL < 0, so this looks feasible

r(Rb+) = 149 pm r(H-) = 146 pm

 Past Paper Question

NH4++ H-(g)

-871 kJ mol-1

NH3(g) + H+(g) + H-(g)

ΔHL of NH4H
-78 kJ mol-1
NH3(g) +H+(g) + e- + H(g) -737 kJ mol-1

+1312 kJ mol-1
NH3(g) + 2H(g)

+436 kJ mol-1
NH3(g) + H2(g) NH4H(s)
+62 kJ mol-1

. × ×
ΔHL (NH4H) = 737 kJ mol-1
( )/
ΔHL > 0, so this doesn’t look feasible

r(NH4+) = 146 pm r(H-) = 146 pm

 Past Paper Question

. × ×
ΔHL (NH4F) = 774 kJ mol-1 The calculated lattice enthalpy is 81 kJ mol-1 too small.
( )/

This implies there is an addition contribution to the

bonding not accounted for by the ionic model.
r(NH4+) = 146 pm r(F-) = 133 pm

RbH and NH4F have almost identical ion radius

ratios, yet RbH adopts the rocksalt structure with
F- 6-coordination of the ions and NH4F adopts the
wurtzite structure with 4-coordination of the
ions.
NH4+ Why ?

H-F Hydrogen bonding!

This also explains why the lattice enthalpy of
NH4F is larger than calculated
 Summary

We can understand the stabilities of simple ‘ionic’ compounds using ionic model calculations.

We can account for small amounts of covalency by using thermochemical radii rather than crystallographic radii.

The lattice enthalpies calculated are not an exact match for experimental values, but they generally get the ordering
of compound stabilities correct.

Stability of metal hydrides decreases down groups, as lattice enthalpy is the dominant term.

The stability of compounds containing complex anions (CO32-, NO3-, etc.) with respect to the corresponding oxides
increases down groups but decreases with increasing cation charge.

Cations with small radii and high charges will tend to form oxides rather than peroxides or superoxides.