G. J.
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
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
predicted the properties of these missing elements with
remarkable accuracy.
More recently, crystal chemistry has provided a
more quantitative basis for predicting chemical syn-
theses. An early example of this is provided by the
work of Grimm and Herzfield (8) where use was made of
lataticeenergies of neighboring stable compounds in the
periodic table and, for some compounds, values calcu-
lated from the Born-Lande equation (3):
where U is the lattice energy, N is Avogadro's number,
M is the Madelung constant, z+ and z- are the valen-
cies of the ions, e is the charge on the electron, r is the
interionic distance, and n is the electronic shells repul-
sion exponent.
The various lattice energies were used to predict
the stability of a number of hypothetical compounds.
For example, it was predicted that the monohalides of
the noble gases would be unstable in an ionic lattice and
would decompose into the constituent elements ( 8 ) .
The Born-Lande equation is dependent on an exact
lcnowlcdge of crystal structure and hence of the Made-
lung constant. The same is also true of certain other
equations employed for the calculation of lattice ener-
gies of compounds. One such equation is that of Born-
R l a ~ e r(41,
an improved version of equation ( I ) , where p charac-
terizes the quantum-mechanical repulsion forces act-
ing between the electronic shells of the ions and has the
di~nensionsof length. For most crystals p may be re-
garded as practically constant a t 0.345 A.
The Kapustinskii Equations
For hitherto unknown conlpounds, it is imperative
that a certain crystal structure be assumed before equa-
t,ions of the type of (1) and (2) can be used. Kapustin-
skii (5) regarded such an assumption as unsatisfactory
and proposed an equation with which it was possible to
ext,end the sphere of calculations of lattice energies.
The development of this equation may be traced by
making a slight modification in equations ( 1 ) and ( 2 )
204 / Journal of Chemicol Educofion
(6, 7) to give equat,ions (3) and (4). respectively.
I n both equations, v is the number of ions in the mole-
cule and cr = [ M / ( v / 2 ) ] . The Rfadelung constant,
M, is independent of cr, since it is proportional to the
number of ions in the chemical molecule. However, or
is not identical for different lattice types and Kapustin-
skii (5) found, empirically, that in passing from one
lattice type to another, the change in u was proportional
to the change in interionic distance.
With these modifications and by taking the Gold-
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
with the aid of r, derived by X-ray measurements, and
the Madelung structural factor, M, corresponding to
the given lattice.
Several of the quantities in equation (3) may be
grouped in a single proportionality coefficient sincen
has the average value of 9 and Ne2 = 329.7 kcal per A.
Substitution of these quantities gives rise to the eqna-
tion'
256.luz+z-
U =
(r+ + r-)
kcal per mole
which permits the calculation of the energy of any type
of lattice with the aid of charges and radii only.
Similar transformation of equation (4) which includes
the factor p = 0.345 A, characterizing the quantum
mechanical repulsion forces, gives (8) the equation2
-
U = 287.2vz+z-
(r+ + r-) (r+ + ] kesl per mole
0'345
r-) (6)
An objection (7) to the Kapustinskii equations is the
replacement of r, the interatomic distance, by ( I + +
r-). This is because there are many salts in which the
unlike ions are not touching as, for example, in sodium
iodide where the lattice spacing is determined by con-
tacts between the iodide, I-, ions. Also, the assign-
ment of ionic radii can only be regarded as approximate,
even in the case of the alkali halides (6). I n this latter
respect, it is interesting to recall the statement made
by Gibb and Winnerman (9) that "the actual radius of
an ion is as uncertain as the radius of a fluffy ball of cot-
ton batting."
'Recalculation of the proportionality coefficient gives 25.5.7.
Reealcul.%tionof the proportionality coefficient gives 287 6 .
 Nevertheless, the lattice energies obtained by calcula- Table 1. Lottice Energies (kcal per mole) of the Alkali
tions using these equations compare favorably with Metal Fluorides and Iodides
those derived experimentally (by the Born-Haber Ex~eri- d a l c u l a t e d Values
cycle) and with those calculated from other equations
which take into consideration the lattice types. This (Born- Kapus- aid
Hsber tinskii Sherman Helm-
closeness is well illustrated by the dat,a for the alkali Cycle) Eq. (6) Eq. (1) holtz Huggins
metal fluorides and iodides as shown in Table 1. Where Salt (Ref. 7) (Ref. 8) (Ref. 10) (Ref. 11) (Ref. 13)
comparisons can be made, agreement is also reasonable LiF 241 228 239 240 244
for the transition metal(I1) chalcogenides (Table 2). NaF 216 212 214 215 215
Of course, the above equations cannot be expected KF 192 189 189 190 193
RbF 184 182 181 182 183
to produce values for the lattice energies that are as CsF 171 170 172 174 176
exact as those produced by more extended calculations. LiI 176 171 170 174 176
This is because all contributions to the lattice energy are NsI 165 161 160 164 164
KI 151 147 148 151 152
ignored except for the Madelung term, U M ,arising from RbI 147 141 143 145 148
the electrostatic attraction of the ions, and the repul- CsI 140 135 135 140 143
sive energy term, Un,allowing for the repulsive forces
between the ions. The additional contributions to
equation (2) are described in available literature (6, 7, Table 2. Lattice Energies (kcal per mole) of SomeTransition
15) and generally allow for van der Waals energy and Metollll) Chalcogenides
zero-point energy of the molecules in the crystal. Calculated Values--
However, lattice energies calculated from the refined Kmustinskii
equations do not differ greatly from those obtained by Ex~eri- 'Eas
mental (Moddy & Hare &
the more approximate methods (6, 7,15). (Born- Thomas Brewer
Equation (6) has also been refined by Kapustinskii Haber Ref. 1.9) (Ref. 14) Sherman
and Yatsimirskii (6,16) by the inclusion of an additional MCh . Eo.. (5)
Cvele)
" . . Eo.. (6)
. . Eo.. (1)
. . Eo.. (2)
. . (Ref.
. 10)
term to give MnO 911 931 880 916 890 912
FeO 937 953 899 937 907 944
COO 954 967 908 958 917 950
NiO 974 976 914 974 934 968
ZnO 964 957 901 9i7

although Yatsimirskii in a later publication, quotes a

different quantity for the additional term in equation
(7) which in fact is twice as great (I?), as shown in equa-
tion (8).

Kapustinskii equations when compared with the experi-

For calculation purposes, it is convenient to write equa-
tion (8) in the form
Here again, the additional t e r n does not alter the re-
sults appreciably; the effect of the doubled quantity
in equations (8) and (9) being to increase the calcu-
lated lattice energy of metal(1) halides by 5 kcal per
mole and of the much greater lattice energies of the
met,al(III) halides by 30 kcal per mole.
It is, however, difficult to have a clear idea of the ac-
curacy of these expressions, since direct experimental
computation of lattice energy has rarely been accom-
plished and the accuracy of the magnitudes of the Born-
Haber cycle of operations is also open to question, al-
though these are gradually being improved.
Kapustinskii (6) claims that there is very little point
in further improvement of the expressions for lattice
energy until the values of the ionic radii are known with
greater accuracy, although a sacrifice in accuracy is
more than compensated by the universal application of
the equations to compounds, hypothetical or otherwise,
without knowledge of crystal architecture.
Compounds in their lattices vary from the ideal
ionic state and Yatsimirskii has described proposals for
correcting the low values for lat,ticeenergies given by the
mental (Born-Haber) values (18,lQ).
I n a subsequent discussion on the applicability of
equations (8) and (9), Yatsimirskii (17) claims that
these give, for triply-charged cations with eight elec-
trons in the outer shell, values for the lattice energy
that agree to within 3% of the experimental (Born-
Haber) values. Aluminum(II1) is an exception, the
error reaching 9% for the iodide. For compounds of
the tetravalent elements, the discrepancies are some-
what greater, but exceed 10% only for the iodides.
Since many of the compounds studied have significant
degrees of covalencies in their bonds, the low deviations
are remarkable.
The discrepancies for compounds formed by other
types of cation are considerable and for such com-
pounds, where the cations have the electronic confignra-
tions d6, dl0, and d1°s2,Yatsimirskii (17) has suggested
that the equation
U = Ui+C+E. (10)
is applicable. I n this equation, U is the lattice energy,
U t is that calculated by equations (8) and (9), E , is
the energy of extrastabilization by the crystalline
field, and C is the energy of formation of a partially
covalent bond in the crystal. The significant factor
in the deviations between experimental (Born-Haher)
values and those calculated by equations (8) and (9)
are attributed by Yatsimirskii mainly to C which is
Volume 42, Number 4, April 1965 / 205
shown to be a function of the ionization potential and
electron &nity of the cations and anions, respectively,
in the crystal lattice. Introducing corrections along
these lines has brought the agreement between experi-
mental and calculated lattice energies to +2%.
Of course, these corrections for covalency introduced
by Yatsimirskii, follows the practice of several authors
of using the low calculated values of lattice energies
compared with the high (Born-Haber) experimental
values to indicate the deviations from heteropolarity
(7).
Applications of the Kapustinskii Equations
The applications of the ICapustinslui equations have
been varied and apart from a check on the thermo-
chemical data, the equations have opened up wider
horizons for the extension of the evaluation of lattice
energies to ionic crystals not yet investigated by X-ray
measurements, and frequently to compounds not yet
prepared. Before discussing these more obvious appli-
cations, there is the other use, where reliable thermal
data are available, of calculating the radii of ions. Such
a calculation is possible where the radius of either the
cation or anion is lacking. The radii calculated in
this way have heen termed "thermal" or "thermo-
chemical radii" (6).
An example of a radius thus evalu?ted is that of
theSnZ+ion, found to be 1.04 =t0.02 A as determined
from the experimental lat,tice energies of tin(I1) sul-
fide, oxide, and chloride (6). However, the lattice of
these tin compounds vary from the ionic and, as noted
above and as is apparent by inspection of Table 2,
compounds with covalent tendencies give low lattice
energies as computed from the Kapustinskii equations
when compared with the experimental (Born-Haber)
values. On making allowance for this feature, the
value of 1.17 A calculated by Yatsimirskii is probably
more realistic (19).
Equation (6) has been used to calculate the thermo-
chemical radii of a large number of complex ions and
radicals. Values for a selection of anions, assumed
to have spherical symmetry are shown in Table 3.
There are, however, many ions where the structure
is far from spherical. For these, "effective" ionic
radii have been determined by equation (6) and the
"effective thermochemical ionic radius" of the [Ba-
(H2O)IZ+ion has been found to be 1.61+0.01 A from
various monohydrates of barium containing a range
of anions of previously known dimensions, for example,
the halides, nitrate, cyanide, and chlorate (6).
Direct measurement of electron sffinities is difficult
and has only been done for a few elements. To over-
come this problem, an important application of cal-
culated lattice energies is in the evaluation of electron
affinities. Comparison of the values thus obtained
for halogen atoms with those measured by comparing
the rates of negative ion and electron emission from a
heated surface in the halogen vapor, and in other ways,
shows close agreement (15). The lattice energy of
sodium telluride, determined from equation (5) above
Table 3. Therrnochernical Radii of Tetrahedral Anions (6)
Ion 504'- CrOF C101-
Radius (A) 2.30 2.40 2.36
206 / Journal of Chemical Education
has been used to evaluate the electron affinity of the
telluride, TeZ-, ion (IS) :
Te(,.) + 2e = Te2-l.,.l; AHgrs= 64 kesl
The Born-Hober Cycle
Although proton affinities and the enthalpies of
formation of complex ions can be evaluated, the prin-
cipal use of the lattice energies derived from the Kapus-
tinskii equations, both in the original and refined forms,
has been in the prediction of the stability of various
hypothetical compounds (IS, 20, 21, 22, 23). The
various derivations from the lattice energies, including
those of electron affinities, are made with the aid of
the Born-Haber thermodynamic cycle of operations
(24, 25). This is based on the first law of thermody-
namics, and for a crystalline uni-univalent salt, M X ,
may he represented by the scheme
Mx1.1
(i)
Mf(O1 + X-(,)
T I
The first step, (i), is the complete breakup of the
crystal, M X , into gaseous ions M + and X-, attended
by an increase in the heat cont,ent which is the lattice
enthalpy, U +
2RT. For practical purposes, the
quantity 2RT is neglected, being only about 1.2 kcal
per mole a t 29S01<. Thus, the increase in heat content
corresponds to the lattice energy, U .
The second operation, (ii), is the simultaneous dis-
charging of the metal ion, If+, by union with electrons
to give gaseous metal atoms, M, and of the X- ions,
by removal of electrons to give X at,oms. This stage
is attended by an increase in the heat content corre-
sponding to (E - I),where E is the electron affinit,y
of the X atom and I is the ionization potential of the
metal atom.
I n the third step, (iii), the gaseous metal is condensed
to the solid state and X atoms are combined to X9
molecules, and is attended by an increase in heat con-
tent (-3 -'lzD), where S is the heat of sublimation
of the metal and D is the heat of dissociation of
molecular 1%.
The final step, (iv), corresponds to the interaction
of the solid metal with gaseous Xz molecules, that is,
in the forms they normally obtain at 298'1<, to reform
the crystalline salt, =I. The attendant increase in
heat content, AH,, is the enthalpy of formation of the
crystalline salt, M X . Apart from AH,, all the other
quantities referred to in the cycle are also expressed
in terms of 298'Ii.
It follows from Hess's law of constant heat sum-
mation that
U+E-I-S-1/2D+AHI=0 (11)
and hence that the value of any one quantity may be
calculated provided the other five are known.
MnOl- PO4'- BF6- BeF,'- BiOP
2.40 2.38 2.28 2.45 Io4-
2.49 2.68
 Where proton affinities are required, the cycle is
varied slightly as illustrated by the following scheme
for the proton aflinity of ammonia from ammonium
chloride (26).
borofluoride ion, BF4-, in Table 3 may be used to cal-
culate the lattice energies of a range of other boro-
fluorides. These may then be used in a Born-Haber
sequence of operations to calculate the enthalpy of
formation of the borofluoride ion. A suitable Born-
Haber cycle is the following:

The changes in heat content in stages (i) and (iv) have

similar significance t o that described above for the un-
modified Born-Haber cycle. Stage (ii) is broken down Again stages (i) and (iv) have changes in heat content
into two subsidiary stages to cover the breakdown of of similar significance to that of the unmodified Born-
the ammonium, NH4+, ion. Thus (iia) is attended by Haber cycle. The increase in heat content correspoud-
an increase in heat content corresponding to PNES, the ing to stage (ii) is (-I +
E - AH,) where AHI is the
proton affinity of ammonia, while in stage (iib) the enthalpy change for the reaction (I)
increase in heat content is -I, where I is the ionization
potential of the hydrogen atom. The remaining in-
BFIW F-w BFuK+ +

crease in heat content in stage (ii) is, of course, E, the
electron affinity of the chlorine atom.
Stage (iii) corresponds to an increase in heat content
amounting to
I and E having their usual significance. I n stage (iii)
the heat content increase is (-8 - '/%D- AH^^^,^,,),
the terms having their normal significance.
I t is clear from this cycle that the enthalpy of forma-
tion of the borofluoride ion, AHJBF,,o,- is given by

where DH1and Dcl, are the heats of dissociation of mo-

lecular Hz and Clp, respectively, and AHJ,,~,~,is the and the value obtained by Kapustinskii and Yatsimir-
enthalpy of formation of NHa(,). skii ($7) is -406 kcal per mole. Of course, all the re-
The proton affinity of ammonia is therefore given quired quantities in equation (IS) are readily available
by the relation in the literature except for AHI. It is this quantity
which is obtained from the Born-Haber cycle.
Reaction (I) corresponds to a change of hybridization
of the boron orbitals in boron trifluoride and to the
formation of a new bond to accommodate the fluoride
Using equation (12), a value of 209.4 kcal per mole is ion, F-. The enthalpy change, AHr, corresponding to
derived for the proton affinity of ammonia, the mean
these changes has been calculated to be -76 kcal per
value calculated by applying the four ammonium halides
mole for the borofluoride ion (7).
t,o the Born-Haher sequence being 214 kcal per mole (7).
Similar calculations have been made for the BHI- and
The method has been extended to the calculation of
the proton affinities of other species, such as, NHz-, HF2- ions (7) and the procedure can have general
application to include other species.
NH2-, HzO, OH-, 02-,SH-, and SZ- and it has been
suggested that values could be obtained for methyl- Thermodynamic Derivations Using the Kapurtinskii
amines if the relevant lattice energies were known (7). Equations in Conjunction with the Born-Haber Cycle
Approsinlate values could certainly be obtained if the
lattice energies were calculated by the Kapustinskii As already mentioned, the principal application of
equation (7). the Kapustinskii equations has been in t,be prediction
The thermochemical radius of 2.28 A quoted for the of the stabilities of hitherto unknown compounds.
The application of the equations, and subsequent treat-
ment of the lattice energy by the Born-Haher cycle to
Table 4. Comparison Between Calculated and Experi-
mental Enthalpies of Formation of the First Series Transition
Metal(ll) Chlorides and Oxides (Mn to Zn) Table 5. Comparison Between Calculated and Experi-
(The caloulhted values have been derived from t h e short Khpustinskii mental Enthalpies of Formation of Certain Copper(ll) Halides
esuhtmn (5)) and Chalcogenides
Metal Mn Fe Co Ni Cu Zn (The osloulated values have been derived from the short Kapustinskii
equation ( 5 ) )
Chlorides (MCld
( R e . sn -Hdide (Ref, my .-Chalaogenide (Ref. IS)%
Experimental -82 -78 Chlo- Bro-
(koal per mole) Cnooer ride mide Iodide Oxide Sulfide Selenide
Calculated -73 -59
(koal per mole) Experimental
Oxides (MO) koa1permole)-49 -40 -17 -37 -12 -7
( R d 13) Ca\dsted -8to +31 to +85to - 9 t o +51to +113to
Experimental -64 -55 (keal oer mole) +11 +48 +lo0 2 6 +37 +I04 +I55
(koal per mole) (for Feo.nO) Differences 41 to 71 to 102 t o to 63 to 120to
Calculated -68to -6Oto (kealpermole) 60 88 117 74 116 162
lkcal ner mole) -84 -74
* Experimental values t a k e r f r o m Ref.#Q.
Volume 42, Number 4, April 1965 / 207
 obtain the heat of fonnation, is first of all tested on
known compounds and then applied to hypothetical
species. Such a series of calculations requires a knowl-
edge of cation and anion radii, ionization potentials,
electron affinity, and enthalpies of sublimation and
dissociation appropriate to the compound. This data
is available, or determinable, for several series of com-
pounds and has been used in the manner indicated for
halides (ZZ), and chalcogenides (IS), of the first transi-
tion series and similarly (25, 28) for the lanthanide
compounds.
The next stage in the procedure is to use the appro-
priate enthalpies of formation derived from the lattice
energies and application of the Born-Haher cycle, to
calculate the enthalpy changes of various dispropor-
tionation reactions of which the following constitutes
a series for metal (I), (11), and (111) halides:
Appropriate adjustments must be included for chalco-
genides.
The fundamental property that should be used for
predicting the ability of a reaction to proceed is, of
course, the free energy. However, for reactions in-
volving condensed states only, the enthalpy change
can give an indication of its probable course. Such
predictions may be made for reactions M(I)b and
M(I1)b for the halides and also for M(I)a, M(II)b,
and M(II1)a for sulfides, selenides, and tellurides.
The remaining reactions involve a volume increase
due to gas formation. This results in a consequent
increase in entropy, enhancing the enthalpy change to
give a more negative free energy change, thus increas-
ing the probability of the reaction in the direction
written.
Iinowing the appropriate enthalpy of formation for
t,he hydrogen halide or chalcogenide, enthalpy changes
for hydrogen reductions may also be calculated. For
halides, these may be expressed in the following way,
Table 6. Comparison of Calculated Behavior with Observed Behavior of Chlorides and Oxides of Metals of the First
Transition Series
Element Observed Calculated Observed
208 / Journal of Chemical Educofion
suitable adjustments being made for the chalcogenides.
The agreement between lattice energies calculated
by the Kapustinskii equations (5) and (6) and the
experimental (Born-Haber) values has already been
referred to ahove (Tables 1 and 2). This agreement
naturally reflects itself in the enthalpies of formation
of the compounds and this is illustrated by the data
in Table 4 for the chlorides and oxides of the first
transition series.
The calculated values in Table 4 represent the differ-
ence between two large quantities (600 for the chlorides
and around 900 for the oxides) and in view of this, the
agreement is good. It is to be noted, however, that the
agreement is less good for the copper compounds.
This is attributed to the more covalent character and
in agreement with this view, the discrepancies are even
greater for the iodide (22) and selenide (IS) where, of
course, the polarizability of the anion is increased.
The increasing difference between the calculated and
experimental values with increased polarizability of the
anion is apparent from Table 5 .
It is seen from Table 5 that the sequence is regular
thus giving support to the fact that some covalent
binding is involved. The differences are particularly
great for the copper compounds which are known to b?
distinctly covalent in character, hut are not so pro-
nounced for other series, for example, the difference is
between 4 and 20 kcal per mole for iron(I1) oxide and
between 63 and 83 kcal per mole for iron(I1) selenide.
Predictions made on the basis of the reactions quoted
ahove are concerned with interconversions of the
various species between different oxidation states of the
metal constituent and, for this reason, there will he
some cancellation of errors (15, t3). I n fact, predic-
tions made on the basis of enthalpy changes determined
from the Kapustinskii equations and the Born-Haher
cycle have led to good agreement with fact. This is
illustrated by the data for chlorides and oxides of
metals of the first transition series in Table 6.
Calculated Observed Cdeulated
 Except for the copper compounds, the theoretical iodides of promethiurn(I1) aud t.huIium(I1). All these
predictions are in close agreement with experimental halides are known, as are also many others, including
fact and on this basis it has been suggested that it some fluorides, which are indicated by the calculations
might be worth while investigating the possibility of to be rather less stable (32).
preparing scandium(I1) bromide and iodide (22), With regard to the lanthanide(I1) chalcogenides,
scandium(I1) oxide, sulfide, and selenide (IS) and the selenides and tellurides of europiurn(I1) and yt-
nickel(II1) fluoride (22). Successful syntheses fol- terbium(II), and the tellurides of promethium(II),
lowing predictions from lattice energy calculations, samarium(II), and thulium(I1) are stable according
have, of course, been accomplished by Yatsimirskii (20) to the calculations (SO) and, except for the promethium
as long ago as 1948. compound, all are known (32). In addition, a range
of other lanthanide(I1) selenides and tellurides as
Stabilities of Lanthanide Halides and Chalcogenides
well as of oxides and sulfides are known (32) and from
Novikov and Polyachenok (23) have recently re- the trends (SO) it is apparent that many more await
ported a similar series of calculations, using lattice discovery.
energies determined by equation (8). These, cou- Rough estimates by Novikov and Polyachenok (23)
fined to lanthanide(I1) and (111) chlorides, confirm indicate that the monochlorides of the lanthanides are
the stability of the chlorides of samarium(II), eum- unstable in the solid and liquid states.
pium(II), and ytterbium(I1). Arising from this work, The possibility of preparing the dichlorides of the
it has been suggested that stable chlorides of prome- lanthanides by hydrogen reduction of the trichloride
thium(I1) and thulium(I1) may be obtained and, in (reaction M(1II)c) has also been studied (23) and the
addition to the less stable neodymium(I1) and praseo- results indicate practically complete reduction in the
dymium(I1) chlorides, it may also be possible to obtain case of the chlorides of samarium(III), europium(III),
the chlorides of dysprosium(II), holmium(II), and and ytterbium(II1) in accordance with practice. Par-
erbium(I1). While confirming the known stabilities tial reduction is indicated for the chlorides of neo-
of the lanthanide(II1) chlorides, the calculations do dymium(III), promethium(III), dysprosium(III),
not anticipate the formation of chlorides of lanthanum- holmium(III), erbium(III), and thulium(II1).
(11), cerium(II), gadolinium(II), or terbium(I1).
The calculations, using lattice energies derived from Lattice Energies and Crystal Field Stabilization
equation (6) (equation (8) increases these by about
3 per cent), have now been extended to include all the Reference has already been made above to the differ-
lanthanide(I1) and (111) halides and chalcogenides (SO). ences between experimental (Born-Haber) and calcu-
Table 7 illustrates the remrliable agreement between lated lattice energies being used to indicate deviations
the enthalpies of formation of the lanthanide(II1) from strict heteropolarity. There is another effect
oxides thus obtained and the literature (31) values. responsible for deviations, and is present in those
With the possible exception of ytterbium(II1) sele- crystals in which the metal ion has an unfilled d shell.
nide and the tellurides of samarium(III), europium(II1) Under the influence of the electrostatic field of the
and ytterbium(III), the enthalpy changes accompany- neighboring negative ions, the otherwise five-fold
ing reactions M(I1)b and M(II1)a confirm the known degenerate electron energy levels of the metal ion are
stabilities of the lanthanide(II1) halides and chalco- split to several new levels, depending on the symmetry
genides. The magnitudes of the enthalpy changes
of the crystal field, and the electrons first occupy the
also indicate that several of the lanthanide(I1) com- lowest levels in preference to the higher ones. This
pounds should be stable. These include the chlorides,
splitting produces a stabilization energy known as the
bromides, and iodides of europium(I1) and ytterbium- crystal field stabilization energy (c.f.s.e.).
(11), the bromide and iodide of samarium(II), and the
Several authors (33, 34, 56, 36, 37, 38) have drawn
attention to the fact that if the experimental (Born-
Haber) lattice energies of the divalent transition metal
Table 7. Comparison Between Calculated* Eq. (6) and
halides are plotted against their atomic number, a
Literature* Values of the Enthalpies of Formation of Lantho- minimum occurred a t the manganese(I1) salt. I n
nide(lll) Oxides (Lnz03) fact, by taking the change in energy as zero when the
(Values are in koal per male LnzOa) number of d electrons is 0,5, or 10 and drawing a smooth
Element La Ce Pr Nd curve through the lattice energies of the calcium, man-
Calculated* -400 to -396to -408 to -403 to ganese, and zinc salts, the c.f.s.e.'s are obtained as the
-448 -444 -456 -451 difference between the points on the smooth curve and
Literature* -428 -434 -436 -432
the actual experimental (Born-Haber) lattice energies.
Element Pm Sm Eu Gd Using this procedure, Yatsimirskii (36) on taking
Calculated* -414to -424to -433 to -428 to
-462 -472 -481 -476 the hydroxides, fonnates, oxides, carbonates, sulfates,
Lit,watureY -434 -434 -434 -434 chlorides, bromides, and iodides, found values of 9,
Element Tb DY Ha Er 30,32, and 27 kcal permole, respectively, for the c.f.s.e.'s
Cdculated* -431 to -468 to -446 to -432 to of iron(II), cobalt(II), nickel(II), and copper(I1).
-474 -516 -494 -4xn
These are in close agreement to the values found on
account of the fields of water moleoules (36). Also,
Element Tm Yb Lu the value of 32 kcal per mole for nickel(I1) is very near
Calculated* -418 ta -420 to -399 to
-466 -468 -447 that of 30 kcal per mole, obtained by Ladd and Lee (38)
Literature -452 -434 -450 in an independent but similar set of calculations. Com-
'Calculated Ref. $0. Literature Ref. $1. pounds from other sets of anions give different c.f.s.e.
Volume 42, Number 4, April 1965 / 209
 values, for example, the selenide and fluoride ions in importance of lattice energy as a fundamental property
nickel(I1). - give values in excess of 40 kcal Der mole is thus confirmed, and the realization of this in recent
(36,278). years has led to increasing attention being given to
It has been found for fluorides of the metals of the the subject in modern textbooks.
first transition series that, after allowing for the c.f.s.e., The authors are grateful to J. M. Crahtree for Rus-
there is little difference between the calculated lattice sian-English translation services.
energies and those obtained experimentally through
the Born-Haber cycle (7). Discrepancies are large for Literature Cited
bromides and iodides and cannot be explained by the (1) MENDELEEV, D. I.. "Principles of Chemistry," 1905, p. 30.
c.f.s.e. (7). (2) GRIMM,H. G., AND HERZFIELD, K. F., Z. Physik., 19, 141
Hare and Brewer (14) attempted to explain the devia- (1923).
tions between the lattice energies of the transition (3) BORN,M., AND LANDE,A., Verhandl. deut. physik., Ges., 20,
210 (1918).
metal oxides calculated by the Born-Lande and Born- BORN,M., *ND MAYER,J . E., Z. Physik., 75, 1 (1932).
Mayer equations (5 and 6) from the experimental KAPUSTINSKII, A. F., Z. Phus Chem., ZZB, 257 (1933).
(Born-Haber) values on the basis of c.f.s.e., hut had to KAPUSTINSKII, A. F., Q ~ r tRev.,
. lo, 283 (1956).
conclude that no simple theory gives a precise explana- WADDINGTON, T. C., "Advances in Inorganic and Radio-
tion of the variation. Doubtless, the complicating chemistry" (Editom: EMELEUS,H. J., A N D SHARPE,
A. G.), Academic Press, New York, 1, 157 (1959).
effects of the deviations from heteropolarity cannot be KAPUSTINSKI& A. F., Ada Phvsicochim., 18, 370 (1943).
ignored in many of these series of compounds. GIBB,T. R. P.,AND WINNEWAN,ANNE,J. CHEM.EDUC.,
35. 578 (19581.
J., hen. Rev., 11, 93 (1932).
SHERMAN,
Lattice Energies and the Oxidation State of MAYER,J. E., AND HELMHOLTZ, L., Z. Physik., 75, 19
Metals in Their Fluorides and Oxides - - - - ,.
(1QR2\
\

(12) HUGGINS, M. L., J. C h m . Phys., 5, 143 (1937).

The formation of a compound from its elements (13) ~ ~ O O D G.YJ.,
, AND THOMAS, J . D. R., J. C h m . Soc., 1417
(1964).
depends on a free energy decrease for the process. To (14) HARE,P. H., AND BREWER, L., Report of Contract W.7405-
a large measure, this is related to the enthalpy change, eng-48, Univ. of California Radiation Lab. (1955).
which, as shown by equation ( l l ) , is dependent on the (15) GLASSTONE, S., "Textbook of Physical Chemistry," 2nd
magnitude of the lattice energy. Inspection of equa- ed., D. Van Noststrand Co. Ino., New York, 1946.
(16) KAPUSTINSKII,A. F., A N D YATSIMIRSKII, K. B., ZhW.
tion (11) shows that, since ('/*D- E) is about -60 Obshch. Khim., 26, 941 (1956).
kcal per gram atom for the halogens, the factor mainly (17) YATSIMIRSKII, K. B., Zhur. Neorg. Khim., 6, 518 (1961).
responsible for the magnitude of the enthalpy change, (18) YATSIMIRSKII, K. B., "Thermachemistry of Complex Com-
in a series of halides, is in fact the lattice energy. I t is pounds," (Editor: KAPUSTINSKII, A. F.), U.S.S.R.
not surprising, therefore, that since the lattice energies Academy of Sciences, Moscow, 1951.
of the fluorides are greater than for the other halides, (19) YATSIMIRSKII. , . ~ .,
K. B.. Zhur. Obshch. Khim.. 23. 180 (19531.
(20j YATSIMIRSKII; K. B:, ~tvestlAkad. Nauk. S.S.S.R., Oldel.
most met,als show their highest oxidation states in the Khim. Nauk, 263 (1948).
fluorides. (21) KAPUSTINSKII, A. F., AND VAVER,V.,ibid., 631 (1951).
Oxides also frequently exhibit the highest oxidation (22) BARBER, If., LINNETT,J. W., AND TAYLOR, N. H., J. Chem.
states of metals. However, here the advantage gained Soc., 3323 (1961).
(23) N ~ V I K U G.V , I., A N D POLYACHENOK, 0. G., Zhur. Neorg.
in having a much greater lattice energy than for the Khim., 8, 1567 (1963).
fluorides is mainly lost in the positive character of (241 BORN.M.. Verhandl. deut. uhvaik. Ges.., 21..13 (19191.
, ,
(I/%D - E) a t the rather large value of about +220 (25j HABE;, F:, ibid., 21, 750 ( i g i ~ ) .
kcal per gram atom of oxygen. (26) GRIMM,H. G., Handbueh d. Physik, 24, 518 (1927).
(27) KAPUSTINSKII, A. F., AND YATSIMIRSKII,K. B., ZhW.
Obshch. Khim., 19, 2191 (1949).
Conclusion (28) IIooou, G. J., AND THOMAS, J. D. R., Unpublished work.
(29) LATIMER,W. M., "Oxidation Potentials," 2nd ed., Prentice-
Hall, Inc., New York, 1952.
Among other applications of lattice energy calcula- (30) MOODY, G. J., AND THOMAS, J. D. R., Unpublished work.
tions may be cited the formulation of dioxygenyl hexa- (31) WESTRUM, F., AND JUSTICE, H., "Rare Earth Resesrch-
fluoroplatinate (279) as 02+[PtF6]-and also the similar Proceedings of the Second Conference on Rare Earth
formulat,ion of the analogous xenon conlpound (40, 41) Research," (Editors: NACHMAN, J. F., AND LUNDIN, C. E.),
Gordon and Breach, New York, 1961, p. 161.
through lattice energies calculated by the Kapnstinskii (32) COTTON,F. A,, A N D WILKINSON, G., "Advanced Inorganic
procedure. Chemistry," John Wiley and Sons, Inc., New York, 1962.
Apart from applications in predicting the existence (33) ORGEL,L. E., PTOC. 10th Solvay C a f . Chem., Brussels, p. 289,
of hitherto unknown compounds, lattice energy calcula- (1956).
(34) GRIFFITH,J . S., AND ORGEL,L. E., Quad. Rev., 11, 381
tions, by equation (6), and subsequent operation of the (1957).
Born-Haber cycle have recently been used to determine (35) HUSH,N. S., A N D PRYCE,I f . N., J. Chem. Phys., 28, 244
the likely enthalpy of formation of platinum(I1) fluo- IlRSR>.
\----,.
ride, the existence of which was doubted (48). The (36) YATSIMIRSKII,
K. B., Zhw. h'eo~g.Khim., 3, 2244 (1958).
value derived was about 30 kcal per mole and attempts (37) ORGEL, L. E., "An Introduction to Transitian-Metal
Chemistry," Methuen, London, 1960.
to confirm the existence of the difluoride have proved . . LADD,hZ. F. C., A N D LEE, W. H., J. Chem. SOL, 2837
(38)
to be unsuccessful in agreement with the positive value (1962).
obtained (42). (39) BARTLETT, N., AND LOAMANN, D. H., ibid., 5253 (1962).
I t is clear that the Kapustinsliii method of estimating (40) BARTLETT, N., Proe. Chem. Soc., 218 (1962).
the lattice energy from ionic radii, together with subse- (41) MOODY, G. J., AND THOMAS, J. D. R., "Noble Gases and
their Compounds," Pergamon Press, Ltd., Oxford, 1964.
quent application of the Born-Haher cycle, has proved j42) BARTLETT, N., A N D LOAMANN, D. H., J . Chem. Soc., 619
to he extremely useful in inorganic chemistry. The (1964).

210 / Journal of Chemical Education