Ionic Model and Structures of Solids

M. A. Hayward

Ionic Model Lecture 3:

• Thermodynamic stability of different oxidation states.

• Analysis of the possibility of oxidation of Group I metals to the M2+ oxidation state.
• Instability of Group II mono-halides to disproportionation.
• Stability of transition-metal halides.
• ‘Oxidizing power’ of different non-metals.
 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)
AgCl adopts the rocksalt structure. Diffraction
- 368 kJ mol-1 measurements reveal the lattice parameter is
554pm, thus r(Ag+) + r(Cl-) = 277pm.
Ag+(g) + e-(g) + Cl(g)
. ×
ΔHL (in kJ mol-1)
+ 122 kJ mol-1 ( )/
ΔHL (AgCl) We can calculate the lattice enthalpy of AgCl
Ag+(g) + e-(g) + 1/2Cl2(g) + 897 kJ mol-1 using the Kapustinskii equation.
. × ×
+ 730 kJ mol-1 ΔHL = 779.7 kJ mol-1

Ag(g) + 1/2Cl2(g) The mismatch between observed and

calculated lattice enthalpy values arises from
+ 286 kJ mol-1 interactions outside the ionic model :
covalency.
Ag(s) + 1/2Cl2(g) AgCl(s)
- 127 kJ mol-1

We can account for this ‘extra’ bonding interaction by adjusting the radii of the ions.

. × × Thus the sum of the thermochemical radii

ΔHL = 897 kJ mol-1
( )/ r(Ag+) + r(Cl-) = 240 pm.
 Group I Metals

Can we use the ionic model to understand which metal oxidation states are accessible, and which are not ?

From our previous analysis of Group 1 metal compounds it is clear that all the Group 1 metal mono-halides (MX)
are thermodynamically stable. That is to say they all have ΔHf < 0.

This is because the lattice enthalpy of MX is greater than the sum of the atomisation enthalpy and 1 st ionization
energy of the metal, with the atomization energy and electron affinity of the halogen.

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

-246 kJ mol-1
. ×
Na+(g) + e-(g) + Cl2(g) ΔHL (in kJ mol-1)
( )/
- 763 kJ mol-1
+ 502 kJ mol-1 r(Na+) = 102 pm, r(Cl-) = 181 pm
Na(g) + Cl2(g) ΔHL (NaCl) = 763 kJ mol-1
+ 107 kJ mol-1

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

- 400 kJ mol-1

It is clear that NaCl is thermodynamically stable with respect to the elements,

but can we make NaCl2 ?
 Group I Metals

Na2+(g) + 2 Cl-(g)

-246 kJ mol-1
The 2nd ionization energy of sodium is huge!
Na2+(g) + e-(g) + Cl-(g) + 1/2Cl2(g)
+ 4652 kJ mol-1

Na+(g) + Cl-(g) + 1/2Cl2(g) -ΔHL(NaCl2)

-246 kJ mol-1
Na+(g) + e-(g) + Cl2(g)
- 763 kJ mol-1
+ 502 kJ mol-1

Na(g) + Cl2(g)

+ 107 kJ mol-1
ΔHf (NaCl) ΔHoxidation
Na(s) + Cl2(g) NaCl + 1/ Cl NaCl2(s)
(s) 2 2(g)
- 400 kJ mol-1

For ΔHf (NaCl) to be exothermic

+1229ΔH mol-1 > ΔHatom(Na) + 1st IE(Na) + ΔHf (Cl- )
kJL(NaCl)

For ΔHf (NaCl2) to be exothermic ΔHL(NaCl2) > ΔHatom(Na) + 1st IE(Na) + 2nd IE(Na) + 2ΔHf (Cl- )

The Kapustinskii equation tells us that ΔHL(NaCl2) ~ 3 × ΔHL(NaCl) but this doesn’t look like it will be big enough
 Group I Metals

Na2+(g) + 2 Cl-(g)

-246 kJ mol-1
. ×
Na2+(g) + e-(g) + Cl-(g) + 1/2Cl2(g) ΔHL (in kJ mol-1)
( )/
+ 4652 kJ mol-1
r(Na+) = 102 pm, r(Cl-) = 181 pm
Na+(g) + Cl-(g) + 1/2Cl2(g)
- 2289 kJ mol-1 If we assume r(Na2+) = r(Na+) which isn’t
-246 kJ mol-1 likely, but is a good starting point, then:

Na+(g) + e-(g) + Cl2(g) ΔHL (NaCl2) = 2289 kJ mol-1

+ 763 kJ mol-1
+ 502 kJ mol-1
Thus ΔHoxidation = +2880 kJ mol-1
Na(g) + Cl2(g)
So using the radius of Na+ in place of the
+ 107 kJ mol-1 radius of Na2+ we see the formation of
ΔHf (NaCl) ΔHoxidation NaCl2 is strongly endothermic.
Na(s) + Cl2(g) NaCl + 1/ Cl NaCl2(s)
(s) 2 2(g)
- 400 kJ mol-1 +2880 kJ mol-1

+2480 kJ mol-1
 Group I Metals

It is clear our analysis shows that NaCl2 is not stable, but could this be due to our assumption that r(Na2+) = r(Na+) ?

How small would Na2+ have to be the make NaCl2 stable?

ΔHf (NaCl) ΔHoxidation

Na(s) + Cl2(g) NaCl(s) + 1/
2Cl2(g) NaCl2(s)
- 400 kJ mol-1

ΔHf (NaCl2)

In order that NaCl2 is stable, it is not sufficient for ΔHf (NaCl2) < 0, as this just indicates NaCl2 is more stable than
the elements. We need ΔHf (NaCl2) < -400kJ mol-1, which means ΔHoxidation < 0 so that NaCl2 is more stable than
NaCl + ½ Cl2.

ΔHf (NaCl2) = 0 Na(s) + Cl2(g)

Na(s) + Cl2(g) NaCl2(s)

NaCl(s) + 1/2Cl2(g) NaCl(s) + 1/2Cl2(g) NaCl2(s)

ΔHoxidation = 0
 Group I Metals

Na2+(g) + 2 Cl-(g)

-246 kJ mol-1
If ΔHoxidation < 0
Na2+(g) + e-(g) + Cl-(g) + 1/2Cl2(g) ΔHL(NaCl2) > 5169 kJ mol-1.
+ 4652 kJ mol-1
1.08 × 10 × 6
ΔHL(NaCl2) =
Na+(g) + Cl-(g) + 1/2Cl2(g) ( )+ ( )
-ΔHL(NaCl2)
-246 kJ mol-1 This means that r(Na2+) + r(Cl-) < 125pm
Na+(g) + e-(g) + Cl2(g)
+ 763 kJ mol-1 This is smaller than the radius of Cl-, (181pm)
+ 502 kJ mol-1 so it is clear NaCl2 cannot be formed however
small r(Na2+)
Na(g) + Cl2(g)

+ 107 kJ mol-1
ΔHoxidation
Na(s) + Cl2(g) NaCl(s) + 1/2Cl2(g) NaCl2(s)
- 400 kJ mol-1

ΔHf(NaCl2)

While it is clearly not possible to prepare NaCl2 due to the high 2nd ionization energy of sodium, is it possible
to prepare any compound with a Group I metal in the M2+ oxidation state ?
 Group I Metals
Generalizing for any Group I MX2 halide, we require that: ΔHL(MX2) - ΔHL(MX) > 2nd IE(M) + ΔHf (X-)
×6 ×2
> 2nd IE(M) + ΔHf (X-) +
( )+ ( ) ( )+ ( )

So we have the best chance of stabilizing MX2 when r(X-) is smallest and ΔHf (X-) is most favourable: Fluorine.

ΔHf (F-) = -253 kJ mol-1, r(F-) = 133 pm

M r(M+) 2nd IE ΔHL(MF) ΔHL(MF2) Maximum Maximum

(pm) (kJ mol-1) (kJ mol-1) required r(M2+) + r(X-) r(M2+)
(kJ mol-1) (pm) (pm)
Li 76 7298 1033 8078 80 -53
Na 102 4562 919 5528 117 -15
K 138 3051 797 3595 180 47
Rb 152 2632 757 3136 206 73
Cs 167 2420 720 2887 224 91
The required values for r(M2+) are clearly wildly unrealistic. Thus we can see that there are no Group 1
MF2 compounds which are thermodynamically stable.
We can perform the same exercise for the oxidation of M2O to 2MO and get the same result.
Thus we can see that no Group I metal can form a solid with a high enough lattice enthalpy to ‘pay’ for
its second ionization energy.
 Group II Metals
So if we can’t have a Group 1 M2+ cation in a compound, what about a Group II M+ cation ?

Ca+(g) + X-(g) 1.08 × 10 × 2

ΔHL(CaCl) = = 662 kJ mol-1
- 246 kJ mol-1 ( )+ ( )

Ca+(g) + e- + 1/2Cl2(g) r(Ca+) = 145 pm, r(Cl-) = 181 pm

-662 kJ mol-1
+ 590 kJ mol-1
Ca(g) + 1/2Cl2(g) We can estimate the ionic radius of Ca1+ as the
average of the radius of Ca2+ (100pm) and the
+ 178 kJ mol-1 metallic radius (190pm).
1/
We can see that ΔHf would be exothermic as long as
Ca(s) + 2Cl2(g) CaCl(s) r(Ca+) < 232 pm.
-140 kJ mol-1

We can easily demonstrate that CaCl is thermodynamically more stable than the elements, but that is not the
real problem. We have to consider disproportionation :

2CaCl CaCl2 + Ca
 Group II Metals

Ca2+(g) + Ca(s) + 2 Cl-(g) ΔH(1) = 2nd IE(Ca) – 1st IE(Ca) – ΔHatom(Ca) = +377 kJ mol-1
ΔH(1) 1.08 × 10 × 6
ΔHL(CaCl2) ΔHL(CaCl2) = = 2306 kJ mol-1
2Ca+(g) + 2 Cl-(g) ( )+ ( )
r(Ca+) = 100 pm, r(Cl-) = 181 pm
+ 1324 kJ mol-1
The disproportionation of CaCl2 is strongly thermodynamically
2 CaCl(s) CaCl2(s) + Ca(s) favoured. This result is not due to a bad estimate of r(Ca+), the
-605 kJ mol-1
radius Ca+ would need to be < 22 pm to make the
disproportionation endothermic.

CaCl is clearly unstable, but are there any Group II monovalent halides which are stable with
respect to disproportion ?

This would require 2 × ΔHL(MX) + ΔH(1) > ΔHL(MX2)

×4 ×6
( )+ ( )
> ( )+ ( )
- ΔH(1)

This is inequality is most likely to be true for large r(X-) : iodides.

 Group II Metals

We require 2 × ΔHL(MX) > ΔHL(MX2) - ΔH(1)

ΔH(1) = 2nd IE(M) – 1st IE(M) – ΔHatom(M)
r(I-) = 220 pm

M r(M2+) ΔHL(MI2) ΔH(1) ΔHL(MI) Maximum

(pm) (kJ mol-1) (kJ mol-1) required r(M+)
(kJ mol-1) (pm)
Mg 72 2219 565 1654 41
Ca 100 2025 377 1648 42
Sr 118 1917 331 1566 55
Ba 135 1825 282 1543 60

The required values for r(M+) are smaller than the corresponding observed M2+ radii. Thus we can see
that there are no Group II MI compounds which are thermodynamically stable with respect to
disproportionation.
 Transition Metal Halides
Unlike metals in Group I and Group II, transition metals can exhibit multiple oxidation states in ‘ionic’ compounds.
For example a wide variety of transition metal halides are observed to be stable.

Ti V Cr Mn Fe Co Ni Cu

Fluoride 2, 3, 4 2, 3, 4, 5 2, 3, 4, 5, 6 2, 3, 4 2, 3 2, 3 2 2

Chloride 2, 3, 4 2, 3, 4 2, 3, 4 2 2, 3 2 2 1, 2

Bromide 2, 3, 4 2, 3, 4 2, 3, 4 2 2, 3 2 2 1, 2

Iodide 2, 3, 4 2, 3 2, 3 2 2 2 2 1

Can we explain the observed stable phases, and lack of others using the ionic model ?

Transition metal compounds exhibit a large amount of covalent character in their bonding, so we are going to
have to make extensive use of thermodynamic radii to take this into account.
 Transition Metal Halides
We can think of the formation of the transition metal halides as a series of oxidations which convert MXn into MXn+1.

Thermodynamically this equates to the cycle:

M(n+1)+(g) + (n+1)X-(g)

ΔHf(X-) Thus for each oxidation cycle to be spontaneous:

M(n+1)+(g) + e- + nX-(g) + ½X2(g) ΔHL(MXn) + (n+1)th IE(M) + ΔHf(X-) -ΔHL(MXn+1) < 0

-ΔHL(MXn+1)
(n+1)th IE(M)
or
Mn+ (g) + nX- (g) + ½X2(g)
ΔHL(MXn) + (n+1)th IE(M) + ΔHf(X-) < ΔHL(MXn+1)
ΔHL(MXn)
MXn(s) + ½X2(g) MXn+1(s)
× ( + 1)( + 2) × ( + 1)
(n+1)th IE(M) + ΔHf(X-) < -
( )+ ( )
( ( ) )+ ( )
where A = 1.08 × 105

If we make the simplification that r(Mn+) ~ r(M(n+1)+) then

× (2 + 2)
(n+1)th IE(M) + ΔHf(X-) <
( )+ ( )
 MX3 Transition Metal Halides
To determine if a particular MX3 transition metal halide is thermodynamically stable, we need to evaluate the
following inequality:
× (6)
3rd IE(M) < - ΔHf (X-)
( )+ ( )

3rd Ionization Energy

Cu Reminder:

The third ionization energy of the transition metals

3rd Ionization Energy (kJ mol-1)

Ni can be understood by considering two principal

factors:
Mn Co
1) Increase in Zeff across transition series (Z
increases much faster than the shielding)

Cr 2) Exchange energy.
Fe

V
Mn2+ - 10J Mn3+ - 6J
Ti Local maximum in 3rd IE at manganese due to largest
loss of exchange energy.
 MX3 Transition Metal Halides
To determine if a particular MX3 transition metal halide is thermodynamically stable, we need to evaluate the
following inequality:
× (6)
3rd IE(M) < - ΔHf(X-)
( )+ ( )

Thermochemical radii of M3+

Thermochemical radius
of M3+ (pm)

Ti

V Mn Fe
Ni
Cr Co Cu

The thermochemical radii of the M3+ transition metals,

show a general decrease across the series (increasing Zeff )
but there are some important local minima and maxima
due to covalency – see later lecture courses for details.
 Transition Metal Halides
Ti V Cr Mn Fe Co Ni Cu

Fluoride 2, 3, 4 2, 3, 4, 5 2, 3, 4, 5, 6 2, 3, 4 2, 3 2, 3 2 2

Chloride 2, 3, 4 2, 3, 4 2, 3, 4 2 2, 3 2 2 1, 2

Bromide 2, 3, 4 2, 3, 4 2, 3, 4 2 2, 3 2 2 1, 2

Iodide 2, 3, 4 2, 3 2, 3 2 2 2 2 1

× (6)
3rd IE(M) < - ΔHf(X-)
Cu ( )+ ( )
3rd Ionization Energy (kJ mol-1)

Ni
F × (6)
We can plot value of
( )+ ( )
- ΔHf(X-)
Mn Cl
Co
for each of the halogen-metal combinations.
Br
I We see that the size of this value decreases as
Cr Fe the halogens get heavier, due to increased r(X-)
Fe
and less exothermic ΔHf (X-)
V

Ti
 Transition Metal Halides
To determine if a particular MX4 transition metal halide is thermodynamically stable, we need to evaluate the
following inequality:
× (8)
4th IE(M) < - ΔHf(X-)
( )+ ( )

Cu
4th Ionization Energy (kJ mol-1)

Thermochemical radius
Fe Ni

of M4+ (pm)
Mn Co

Cr

V
The thermochemical radii of M4+ are
significantly smaller than M3+.
Ti

The 4th IE increases across series, the local

maximum is now at Fe.
 Transition Metal Halides
Ti V Cr Mn Fe Co Ni Cu

Fluoride 2, 3, 4 2, 3, 4, 5 2, 3, 4, 5, 6 2, 3, 4 2, 3 2, 3 2 2

Chloride 2, 3, 4 2, 3, 4 2, 3, 4 2 2, 3 2 2 1, 2

Bromide 2, 3, 4 2, 3, 4 2, 3, 4 2 2, 3 2 2 1, 2

Iodide 2, 3, 4 2, 3 2, 3 2 2 2 2 1

Cu

× (8)
Fe Ni 4th IE(M) < - ΔHf(X-)
4th Ionization Energy (kJ mol-1)

( )+ ( )

Mn Co F
Mn Co Cl
Again we can plot this value for each cation-
Br
Cr anion combination.
Cr
I
VV

Ti
 Transition Metal Halides

Cu Cu

4th Ionization Energy (kJ mol-1)

3rd Ionization Energy (kJ mol-1)

Ni Fe Ni
F
Mn Cl F
Co Mn Co
Cl
Br Br
Cr
I I
Cr Fe
V
V

Ti
Ti

The two plots show that, of the halogens, fluorine can stabilize the highest transition metal oxidation states.

This oxidizing power comes from a combination of a favourable ΔHf (F-)(g) and small ionic radius.
 Transition Metal Halides

ΔHatom 1st EA ΔHf (X-(g)) R(X-)

(kJ mol-1) (kJ mol-1) (kJ mol-1) (pm)
F +79 -332 -253 133
Cl +121 -364 -243 181
Br +112 -342 -230 196
I +106 -294 -188 220

The combination of the most favourable ΔHf (X-(g)) and the smallest radius mean that reaction with fluorine
liberates the largest amount of enthalpy, thus can overcome the largest ionization energy, making fluorine the
‘most oxidizing’ halogen.

M(n+1)+(g) + (n+1)X-(g)

ΔHf(X-)
M(n+1)+(g) + e- + nX-(g) + ½X2(g)
-ΔHL(MXn+1)
(n+1)th IE(M)
Mn+(g) + nX-(g) + ½X2(g)

ΔHL(MXn)
MXn(s) + ½X2(g) MXn+1(s)
 Oxidizing Power of 1st Row Non-metals
We can consider the same parameters for the 1st row non-metals nitrogen, oxygen and fluorine.

ΔHatom EA ΔHf (Xn-(g)) R(Xn-)

(kJ mol-1) (kJ mol-1) (kJ mol-1) (pm)
F +79 1’ = F- = -253 133
-332
O +249 1’ + 2’ = O2- = +1020 140
+771
N +472 1’ + 2’ + 3’ = N3- = +3636 144
+3164

The formation of nitride and oxide ions is highly endothermic, but N3- and O2- are more highly charged than F-.

We can see which non-metal is more ‘oxidizing’ by considering the anion displacement reactions.

CaO(s) + F2(g) CaF2(s) + ½O2(g) ΔH = -707 kJ mol-1

Ca3N2(s) + 3/2O2(g) 3CaO(s) + N2(g) ΔH = -1737 kJ mol-1

Thus we can see that although O2- and N3- have higher ionic charges and therefore higher lattice energies per
anion, this is not sufficient to overcome their large endothermic formation enthalpies.
 Past Paper Question

Inorganic Chemistry
Prelims June 2012:
 Past Paper Question

The lattice enthalpy of an ionic solid, MX, is the enthalpy change for the process:

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

The Kapustinskii equation is derived by combining the Born-Landé equation, for the lattice energy of an ionic
solid:

with……

Born–Landé Equation
 Past Paper Question
…the observation that 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.
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

If we :
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

 Past Paper Question

The Kapustinskii equation is extremely useful because it allows us to estimate the lattice energy of ionic solid
within 10%, without us knowing the structure of the compound.

In using the Kapustinskii equation we assume the ionic model applies:

• 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.
 Past Paper Question

M3+(g) + 3Cl-(g)

ΔHf (Cl- )

M3+(g) + e- + 2Cl-(g) + 1/2Cl2(g)

-ΔHL(MCl3)
I3 (M)

M2+(g) + 2Cl-(g) + 1/2Cl2(g)

ΔHL(MCl2)
MCl2(s) + 1/2Cl2(g) MCl3(s)
ΔHoxidation

ΔHoxidation = ΔH(MCl2) – ΔH(MCL3) + I3(M) + ΔHf (Cl-)

favourable unfavourable Small and

favourable
 Past Paper Question
ΔHoxidation = ΔH(MCl2) – ΔH(MCL3) + I3(M) + ΔHf (Cl-)

favourable unfavourable Small and

favourable

×3×2×1 −6
ΔH(MCl2) = ( )+ ( ) So we can estimate that ΔH(MCl2) - ΔH(MCl3) ~ ( )+ ( )

×4×3×1 Real value is slightly larger than this as r(M3+) < r(M2+)
ΔH(MCl3) = ( )+ ( )

M = Mg: I3 very large (7732 kJ mol-1) and much larger than ΔH(MCl2) - ΔH(MCl3) => MgCl3 is not stable.

M = Al: I3 is relatively small (2774 kJ mol-1) so ΔH(MCl2) - ΔH(MCl3) is favourable enough to overcome
ionization energy and AlCl3 is thermodynamically stable.

So why is AlCl2 unstable ?

Disproportionation
 Past Paper Question

2I3 – (I2 + I1) – ΔHatom(Al)

3 Al2+ (g) +6 Cl- (g) 2 Al3+(g) + 6 Cl-(g) + Al(s)

3 × ΔH(MCl2) -2 × ΔH(MCl3)

3 AlCl2(s) 2AlCl3(s) + Al(s)

×3×2×1
ΔH(AlCl2) = ( )+ ( )
−6
3 × ΔH(MCl2) - 2 × ΔH(MCl3) ~
×4×3×1 ( )+ ( )
ΔH(MCl3) = ( )+ ( )

The large gain in lattice enthalpy is sufficient to ‘pay’ for the disproportionation of 3Al2+ -> 2 Al3+ + Al0
so AlCl2 is not stable
 Past Paper Question

Consider the oxidation of a metal cation

Mn+ to M(n+1)+ by halogen X2

M(n+1)+(g) + (n+1)X-(g)

ΔHf(X-) For the oxidation cycle to be spontaneous:

M(n+1)+(g) + e- + nX-(g) + ½X2
ΔHL(MXn) + (n+1)th IE(M) + ΔHf(X-) -ΔHL(MXn+1) < 0
-ΔHL(MXn+1)
(n+1)th IE(M)
or
Mn+ (g) + nX- (g) + ½X2
ΔHL(MXn+1) - ΔHL(MXn) + ΔHf(X-) > (n+1)th IE(M)
ΔHL(MXn)
MXn(s) + ½X2(g) MXn+1(s)
Gain in lattice enthalpy
 Past Paper Question

ΔHL(MXn+1) - ΔHL(MXn) + ΔHf(X-) > (n+1)th IE(M)

Gain in lattice enthalpy

× ( + 1)( + 2) × ( + 1) × (2 + 2)
Gain in lattice enthalpy = - ~
( ( ) )+ ( ) ( )+ ( ) ( )+ ( )

Maximum for smallest r(X-) -> fluoride

ΔHf(X-) is most favourable for fluoride

We can perform a similar analysis for chalcogenides : X2- (oxide, sulfide, etc.)
× (2 + 3)
From these cycles we can determine that the gain in lattice enthalpy ~
( )+ ( )

While this is more favourable than the lattice energy gain on oxidation with a halogen, the enthalpies of formation
of X2- (O2- , S2- etc.) are strongly endothermic so the chalcogenides are less oxidizing the fluorine.
 Past Paper Question

3 M+(g) + N3-(g)

ΔHf(N3-)
3 M+(g) + 3e-(g) + ½N2(g)
-ΔHL(M3N)
3 × I1(M)
3 M(g) + ½N2(g)
These terms are small
3 × ΔHatom(M) relative to the others
3 M(s) + ½N2(g) M 3N
ΔHtotal ΔHtotal = 3 × [ΔHatom(M) + I1(M)] + ΔHf(N3-) -ΔHL(M3N)

ΔHf(N3-) is very endothermic as it involves breaking

the very strong N-N triple bond.

×4×3×1
ΔHL(M3N) = ( )+ ( )

Only Li+ is small enough to yield a ΔHL(M3N) which

is sufficiently exothermic to overcome the large
endothermic ΔHf(N3-)
 Summary

• The very large second ionization energy of Group 1 metals means that the M2+ oxidation state is never
observed.

• Compounds containing Group II metals in the M1+ oxidation state tend to be unstable with respect to
disproportionation. Thus no Group II MX halides are known.

• The observed transition metal halide compounds can be explained on the basis of the variation in ionization
energies across the transition metal series and the ‘oxidizing power’ of the different halogens.

• The oxidizing strength of non-metal elements is a combination of the formation enthalpy of their anion
(ΔHatom + Electron affinity) and the lattice enthalpy of the compound formed (dependant of r(Xn-))

• Fluoride tends to be the most oxidizing of the non-metals as there is a favourable formation enthalpy for F-
and a small ionic radius.