Lattice Energy

Definition
The Lattice Energy U is the energy change when gas phase
ions combine to form a crystal lattice.

E.g. For

Li+(g) + F-(g)  LiF(s) the lattice energy is -1050 kJ mol-1

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Born-Haber Cycle
Hess’s law states that the enthalpy of a reaction is the same whether
the reaction takes place in one or several steps.

HIE
M(g) M+(g)
+
HEA
X(g) X-(g)
HA(M)
½ D(X2) = HA(X) Uo
Hf
M(s) + ½ X2(g) MX(s)

Hf = HA(M) + HA(X) + HIE + HEA + Uo

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Where

IE  ionization energy
 endothermic process
 always  value

EA  electron affinity
 exothermic process

 always  value

HA (M) enthalpy of atomization of metal M = heat of

sublimation
 endothermic process

 always  value
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HA (X) enthalpy of atomization of X

D (X2)  bond dissociation enthalpy = 2xHA (X)

 endothermic process

 always  value

Hfo  standard enthalpy of formation

 can be either endothermic or exothermic
 therefore, value may be  or 

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Determine the lattice energy for NaCl
Hf(NaCl(s)) = -410 kJ / mol; HA(Na) = 107.7 kJ/mol; HA(Cl) = 121.7 kJ/mol;

IE1 = 496 kJ/mol ; HEA = -349 kJ/mol

IE
Na(g) Na+ (g)
+
HEA
Cl(g) Cl-(g)
HA(Na)
½ D(Cl) = HA(Cl) Uo
Hf(NaCl(s))
Na(s) + ½ Cl2(g) NaCl(s)

Hf = HA(Na) + HA(Cl) + IE+ HEA + Uo

Uo = Hf – (HA(Na) + HA(Cl) + IE1 + HEA) )

Uo = -410 – (107.7 + 121.7 + 496 -349)

Uo = - 786.4 kJ/mol

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Determine the lattice energy for CaF2
Hf(CaF2(s)) = -1228 kJ / mol; HA(Ca) = 178 kJ/mol; D(F2) = 158 kJ/mol;

IE1 = 590 kJ/mol ; IE2 = 1145 kJ/mol; HEA = -328 kJ/mol

IE1 + IE2
Ca(g) Ca2+ (g)
+
2HEA
2F(g) 2F-(g)
HA(Ca)
D(F2) = 2HA(F) Uo
Hf(CaF2(s))
Ca(s) + F2(g) CaF2(s)

Hf = HA(Ca) + 2HA(F) + IE1+IE2 + 2HEA +

Uo
Uo = Hf – (HA(Ca) + 2HA(F) + IE1+IE2 +2HEA) )

Uo = -1228 – (178 + 158 + 590 + 1145 +(2x-

328))
Uo = - 2643 kJ/mol

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 Calculating Lattice Energy

U In principle, the lattice energy for a crystal of known structure can be

calculated by summing all the attractive and repulsive contributions to
the potential energy.
For a pair of gaseous ions

Potential energy is negative for the attraction of oppositely charged ions and positive
for repulsion of like-charged ions.

The potential energy arising from repulsions and attractions acting on one reference
ion can be calculated.

Scaled up to a mole of ion pairs (and with a change of sign) this should equal the
lattice energy of the crystal 69
Consider the potential energy arising from attractions and repulsions acting on a central
Na+ ion of NaCl

From Na+:

6 Cl- at a distance r0

e2  6
EC  
4 0 r0

12 Na+ at a distance √2r0

e 2  12
EC 
4 0 r0 2
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 8 Cl- at a distance √3r0

e2  8
EC  
4 0 r0 3

6 Na+ at a distance 2r0

e 6
2
e 6 2
EC  or EC 
4 0 2r0 4 0 r0 4
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 e2  6 e 2  12 e2  8 e2  6 e 2  24
EC       ......
4 0 r0 4 0 r0 2 4 0 r0 3 4 0 r0 4 4 0 r0 5

e2 6 12 8 6 24
EC   (     ....)
4 0 r0 1 2 3 4 5

The series in parentheses converges at a value that defines the

Madelung constant, M

MZ  Z  e 2
EC  ( )
r0 4 0
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The Madelung Constant
 The Madelung constant is derived for each type of ionic crystal structure. It is the
sum of a series of numbers representing the number of nearest neighbors and their
relative distance from a given ion.

 The constant is specific to the crystal type (unit cell), but independent of interionic
distances or ionic charges.
For a mole of ion pairs (N), using the Madelung constant (M), the expression for the
potential energy of an NaCl-type lattice due to Coulombic interactions is:
NMZ  Z  e 2
U ( )
r0 4 0

M
For the NaCl-type lattice M = 1.7476, and for NaCl ro = 280 pm. Using these values, U
(NaCl) = –867 kJ/mol, which is too negative (cf. –786.8 kJ/mol from Born-Haber data).

 Discrepancy arises from assuming ions are point charges.

 Electron clouds of adjacent ions repel each other as they approach one another.

Born proposed that the repulsive (positive) contribution to the potential energy is
given by

NB
U rep  n
r
where B is a constant specific to the ionic compound and n is a power in the range 6 - 12.

 Adding the Born repulsion correction to the Coloumbic term gives

NMZ  Z  e 2 NB
U ( ) n
4 0
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r0 r
U At r = ro the potential energy must be a minimum, so:
  2
 dU   NMZ Z e nNB
  0  n 1
 dr  r0 4 0 r0
2
r

U Solving for B gives

n 1
 MZ  Z  e 2 r0
B
4 0 n
U Substituting for B in the equation for the Coulombic and Born contributions to
potential energy gives the:

Born-Landé equation

NMZ  Z  e 2  1
U 1  
4 0 r0  n
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The value of n can be calculated from measurements of compressibility or estimated
from theory.
For NaCl, n = 9.1 from experiment, and the Born-Landé equation gives Uo = -771
kJ/mol.
In the absence of experimental data, Pauling's approximate values of n can be
used.

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Born-Mayer Equation

 Born-Landé values are approximate.

 Mayer showed that e–r/ρ, where ρ is a constant dependant on the compressibility of

the crystal, gives a better repulsion term than 1/rn.

Using this improved repulsion term leads to the Born-Mayer equation:

NMZ  Z  e 2  
U 1  
4 0 r0  r0 
• ρ = 30 pm works well for all alkali metal halides and other simple cases when ro
values are in pm.

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Derivation of Born-Mayer Equation

NMZ  Z  e 2 r0
U ( )  Be  
r0 4 0
This potential energy passes through a minimum when dU/dr = 0, which occurs at

dU  NMZ  Z  e 2 B  r0 
0  e
dr0 4 0 r0
2


r0
 NMZ Z e 
  2 NMZ  Z  e 2 NMZ  Z  e 2 
Be  
  U 
4 0 r0
2 4 0 r0 4 0 r0
2

Born-Mayer Equation

NMZ  Z  e 2  
U 1  
4 0 r0  r0 
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Kapustinskii's Equation
In the absence of detailed structural data, Kapustinskii's equation1 can be used to
estimate U:

1.202  10 4 VZ  Z   34.5 
U 1    
r  r  r r 
where r+ and r– are ionic radii (m) for the first denominator (in pm for the second
denominator) and V is the number of ions per formula unit (e.g., 2 for NaCl, 3 for
CaCl2).

Kapustinskii's equation has been used with ionic compounds containing polyatomic
ions as a means of calculating their thermochemical radii, in which the ions are treated
as spheres.
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 Applications of lattice energies

1- Estimation of electron affinities:

One method of estimation uses the Born–Haber cycle, with a value for the lattice
energy derived using an electrostatic model.

2- Estimation of standard enthalpies of formation:

For well-established ionic compounds, it is rarely the case that the lattice energy is
known while the standard enthalpy of formation is not.

However, in theoretical studies of hypothetical compounds, one may wish to estimate a

value of ΔfHo(298 K) using a Born–Haber cycle incorporating a calculated value of the
lattice energy.

The earliest example of this method addressed the question of whether it was
conceivable that neon might form a salt Ne+Cl-. On the basis that the size of the Ne+ ion
would be similar to that of Na+, and that NeCl would possess an NaCl lattice, the lattice
energy of NeCl was estimated to be 840 kJ mol-1.
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This leads to a value of ΔfHo (NeCl;s) ≈ +1010 kJ mol
3- Solubility:

The solubilities of salts in water can be rationalized by considering lattice and hydration
enthalpies.

Compounds that contain ions with widely different radii are soluble in water .

Conversely, the least water-soluble salts are those of ions with similar radii.

It is found empirically that an ionic compound MX tends to be very soluble when the
radius of M+ is smaller than that of X- by about 80 pm.

MX(s)  M+(g) + X-(g) ΔH1 −Lattice enthalpy

M+(g)  M+(aq) ΔH2 Solvation
X-(g)  X-(aq) ΔH3 Solvation
________________________________________________
MX(s)  M+(aq) + X-(aq) ΔH4 = ΔH1+ ΔH2 + ΔH4 Dissolution
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 1
H 1   L H  
r r

 1
H 2   hyd H ( M )  
r 1 1
 hyd H ( MX )    
 1 r r
H 3   hyd H ( X )  
r

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If the radius of one ion is small, the term in the hydration enthalpy for that ion will be
large.
1 1
 hyd H ( MX )    
r r
However, in the expression for the lattice enthalpy, one small ion cannot make the
denominator of the expression small by itself.
1
H 1   L H  
r r
 one small ion can result in a large hydration enthalpy but not necessarily lead to a
high lattice enthalpy, so ion size asymmetry can result in exothermic dissolution.

If both ions are small, then both the lattice enthalpy and the hydration enthalpy may be
large, and dissolution might not be very exothermic.

For salts consisting of small ions, the exceptionally large lattice energies apparently
cannot be compensated by the relatively large hydration enthalpies, rendering these
salts less soluble.

For salts of large ions, the lower solubility is rationalized by relatively small hydration
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enthalpies that cannot compensate for the lattice energy.