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