Beruflich Dokumente
Kultur Dokumente
Moody
and J. D. R. Thomas I Lattice Energy and Chemical Prediction
I
Welsh College of
Advanced Technology Use of the Kapustinskii equations
Cardiff, Wales, U.K
and the Born-Haber cycle
The chemist is fascinated to see the (6, 7) to give equat,ions (3) and (4). respectively.
realizat'ion of chemical behavior previously predicted
by t'heoretical reasoning. Mendeleev established the
reasoning by the basic idea that "there must be some
bond of union between mass and the chemical elements"
( I ) . In order that chemical analogies should be pre-
served, he left gaps in his periodic classification and I n both equations, v is the number of ions in the mole-
predicted the properties of these missing elements with cule and cr = [ M / ( v / 2 ) ] . The Rfadelung constant,
remarkable accuracy. M, is independent of cr, since it is proportional to the
More recently, crystal chemistry has provided a number of ions in the chemical molecule. However, or
more quantitative basis for predicting chemical syn- is not identical for different lattice types and Kapustin-
theses. An early example of this is provided by the skii (5) found, empirically, that in passing from one
work of Grimm and Herzfield (8) where use was made of lattice type to another, the change in u was proportional
lataticeenergies of neighboring stable compounds in the to the change in interionic distance.
periodic table and, for some compounds, values calcu- With these modifications and by taking the Gold-
lated from the Born-Lande equation (3): schmidt ionic radii referred to the coordination number
+
6, giving (r+ r - ) for r , and the structural coefficient,
u = 1.745, for roclr-salt type lattices, the same value
is obtained for the lattice energy as by calculating it
where U is the lattice energy, N is Avogadro's number, with the aid of r, derived by X-ray measurements, and
M is the Madelung constant, z+ and z- are the valen- the Madelung structural factor, M, corresponding to
cies of the ions, e is the charge on the electron, r is the the given lattice.
interionic distance, and n is the electronic shells repul- Several of the quantities in equation (3) may be
sion exponent. grouped in a single proportionality coefficient sincen
The various lattice energies were used to predict has the average value of 9 and Ne2 = 329.7 kcal per A.
the stability of a number of hypothetical compounds. Substitution of these quantities gives rise to the eqna-
For example, it was predicted that the monohalides of tion'
the noble gases would be unstable in an ionic lattice and
would decompose into the constituent elements ( 8 ) . 256.luz+z-
The Born-Lande equation is dependent on an exact
U =
(r+ + r-)
kcal per mole
lcnowlcdge of crystal structure and hence of the Made- which permits the calculation of the energy of any type
lung constant. The same is also true of certain other of lattice with the aid of charges and radii only.
equations employed for the calculation of lattice ener- Similar transformation of equation (4) which includes
gies of compounds. One such equation is that of Born- the factor p = 0.345 A, characterizing the quantum
R l a ~ e r(41, mechanical repulsion forces, gives (8) the equation2
-
U = 287.2vz+z-
(r+ + r-) (r+ + ] kesl per mole
0'345
r-) (6)
an improved version of equation ( I ) , where p charac- An objection (7) to the Kapustinskii equations is the
terizes the quantum-mechanical repulsion forces act- replacement of r, the interatomic distance, by ( I + +
ing between the electronic shells of the ions and has the r-). This is because there are many salts in which the
di~nensionsof length. For most crystals p may be re- unlike ions are not touching as, for example, in sodium
garded as practically constant a t 0.345 A. iodide where the lattice spacing is determined by con-
tacts between the iodide, I-, ions. Also, the assign-
The Kapustinskii Equations ment of ionic radii can only be regarded as approximate,
For hitherto unknown conlpounds, it is imperative even in the case of the alkali halides (6). I n this latter
that a certain crystal structure be assumed before equa- respect, it is interesting to recall the statement made
t,ions of the type of (1) and (2) can be used. Kapustin- by Gibb and Winnerman (9) that "the actual radius of
skii (5) regarded such an assumption as unsatisfactory an ion is as uncertain as the radius of a fluffy ball of cot-
and proposed an equation with which it was possible to ton batting."
ext,end the sphere of calculations of lattice energies.
The development of this equation may be traced by 'Recalculation of the proportionality coefficient gives 25.5.7.
making a slight modification in equations ( 1 ) and ( 2 ) Reealcul.%tionof the proportionality coefficient gives 287 6 .
crease in heat content in stage (ii) is, of course, E, the I and E having their usual significance. I n stage (iii)
electron affinity of the chlorine atom. the heat content increase is (-8 - '/%D- AH^^^,^,,),
Stage (iii) corresponds to an increase in heat content the terms having their normal significance.
amounting to I t is clear from this cycle that the enthalpy of forma-
tion of the borofluoride ion, AHJBF,,o,- is given by
Table 6. Comparison of Calculated Behavior with Observed Behavior of Chlorides and Oxides of Metals of the First
Transition Series
Element Observed Calculated Observed Calculated Observed Cdeulated