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Lattice Energy and the Born-Haber Cycle

For a reaction such as


Na(s) + Cl
2
(g) NaCl(s) we want to decide if the
compound will be stable as an ionic salt.
The customary way of doing this is to use a
thermodynamic cycle (an application of Hesss Law).
In this case the cycle is known as the Born-Haber
Cycle
Na(s) + Cl
2
(g) NaCl(s)
Na(g) Cl(g)
AH
sub

BDE
Na
+
(g) Cl
-
(g)
IE EA
AH
f
Lattice
Energy (U)
+
Energy Economics:
exothermic endothermic
EA (usually) AH
sub

BDE
IE
From Hesss Law:
AH
f
= AH
sub
+ IE + BDE + EA + U
What about U?
If AH
f
is to be negative (needed if it is to be a
stable compound), U had better be negative.


How Do We Get the Value of the Lattice Energy?
if know all of the other terms, including AH
f
, then you can
calculate U from U = AH
f
(AH
sub
+ IE + BDE + EA)
if you dont know AH
f
you can estimate U by several
methods
the Born equation
the Born-Meyer equation
the Kapustinski equation

Start by thinking of U as a purely electrostatic term.
Since crystal lattices of ionic compounds have ions of
opposite charge next to one another, energy should be
released when the crystal is formed. The general form of
an electrostatic interaction is:


2
A B
A B
0 AB 0 AB
z e z e
e
V = = (z z )
4 r 4 r
| | | |
| |
| |
| |
\ . \ .
where
zs are the charges on A and B
e is the charge on the electron
4 is one greater than 3
e
0
is the permittivity of the vacuum
r
AB
the internuclear distance in the crystal lattice
To get the total lattice energy you need to sum all of the
electrostatic interactions experienced by a given ion.
Consider the linear crystal shown here:
focus on the red atom - assume it is a cation - then the
green atoms are anions and the blue cations, the
electrostatic interaction is given by
2 ln
2
...)
5
1
4
1
3
1
2
1
1 (
2
...
5
2
4
2
3
2
2
2 2
2 2
2 2 2 2 2
r
z
r
z
r
z
r
z
r
z
r
z
r
z
= + +
= + + +
The total electrostatic energy is then given by:
M
r
z e
r
z e
V
|
|
.
|

\
|
=
|
|
.
|

\
|
=
2
0
2 2
0
2
4
) 2 ln 2 (
4 tc tc
where the term M, called the Madelung constant,
corrects for the geometry of the crystal lattice
The value of M varies from lattice type to lattice type. For
NaCl the value is 1.748 - the next slide shows part of that
calculation.
The geometric Madelung constant is
therefore:
74756 . 1 ...)
3
8
2
12
6 ( M = + =
look at central Cl:
6 Na at distance r
12 Cl at 2
1/2
r
8 Na at 3
1/2
r
etc
(may be slow to converge)
This approach treats the ions as hard spheres, and assumes
100% ionic character to the bonds. Born and Meyer modified
the approach to include additional interactions (primarily
dispersion forces and covalency).
The result was an equation of the form:
AB
2
*
A 0 B
0 AB
N e z z
r
U= 1- M
r
4 r
| |
| |
|
|
|
|
| |
|
\ .
\ .
where r
*
is a parameter that is approximately 34.5pm if r
AB

is in pm. Kapustinski further modified this equation by
noting that M/r did not change much from lattice to lattice.
His equation for estimating U is:
kJ/mol in
r
34.5
1
r
z z 120,200
AB AB
B A
|
.
|

\
|
|
.
|

\
|
=
v
U
v = ions per
formula unit (2
for NaCl)