364 /GENERAL AND INORGANIC CHEMISTRY (PART-)

liquids have been derived from 1, 3-dialkylimidazolium cations with counterions ike
[PFJ, (BF,] and (CF,SO,] which have melting points muchless than 100°C. Lonic liquids
have very low vapour pressure at room temperature and may be used as environment friendly

solvents for many reactions, particularly in catalysis.

Thermalstabilities of ionic solids may be related to their lattice energies, The Gibbs fres
term-be
energies of decomposition of the compounds are mostly dominated by the enthaipy
entropy terms are either negligible or are comparable for similar compounds. Hence a compar-
ison of thermal stability of different compounds is possible by comparing the difference in
lattice enthalpies between the solid reactants and the solid products. The casy thermal decom.
position of some solid metal carbonates illustrates this nicely. The smaller oxide ion provides
a higher lattice enthalpy in the product oxide. Again, the lattice enthalpies of the carbonates
decrease with increasing polarizing power of the metal cation-carbonates of lithium (small
size) and alkaline earth metals (high charge) decompose readily on heating: carbonates of
highly charged cation (Fe*, AIt) are too unstable to exist.
Problem 8.7
Which of the two compounds, MgCO, and CaCO,, is expected to have a higher decomposition
temperature?
Solution: The reaction concerned is : MCO,(6) ’ MO(S) + CO,(g). From the thermodynamic
relation AG = AH°- TAS, the decomposition temperature T, corresponds to T = AHIAS. AH
is determined by the difference of lattice enthalpies of the oxide and the carbonates in respective
cases. AS° may be assumed to be equal for both the decompositions.
Now, CaCO0, has a higher lattice enthalpy than MgCO, owing to efficient packing of the large
CO, ion with the larger Caz+ ion. The lattice enthalpy of MgCO, is further reduced due to en
hanced polarization of the large soft carbonate ion. Hence CaCO, is expected to decompose at a
higher temperature than MgCO,. (Actual temperature:CaCO, 840°C; MgCO, 300°C. Also,SrCO,
1100°C; BaCO, 1300°C).
Similar correlations hold for the stability of oxides and peroxides of the alkali metals (Ch. 18).
The stability of high oxidation states of many elements in their fluorides and oxides may
also be related to the advantage of higher lattice enthalpy. The formation of a solid metal halide
MX, from the lower oxidation state halide MX may be expressed as
MX()+X,ls.4. s) ’ MX,(9) (lor s corresponds to Br/L,)
The forward reaction is favoured by () higher lattice enthalpy, AH,, of MX,(s) due to
higher charge on M* (ii) electron attachment enthalpy, AHpA of the halogen X. (Entropy
changes in the process will be nearly same for all halogens and hence the AH terms will
primarily control AG for the reactions). Now, the forward reaction occurs at the cost of hAH diss
of X, (and AH Sub or AH,vap in case of I, or Br,). The
dominating factor for the
actually lies in the gain of AH, in forming MX,(s). As the radius of the halide ionconversion
increases
from F to I, this gain in lattice enthalpy of MX,(s) over MX(s) becomes
consistent with the observationthat there are no
smaller. This 1s
coresponding iodides for many fluorides:
but not Cul,
CuF? AgF, TIF, Mnf4 VFs
Agl, TII; Mnl4
TI', is known; it is TII,)
 8.3.3 PROPERTIES OF IONIC COMPOUNDS / 365

The highoxidation state of the metals actually causes oxidation of iodide to iodine and the
formation of an iodide of the metal in lower oxidation state.
Chemists have taken advantage of the low lattice enthalpy associated with large ions in
stabilizing many large counter-ions against decomposition. Thus, Cst, N'But etc. ions stabilize
o- Cl, and many other large species; smaller cations do not favour such cases. They would
favour the formation of MBr(s)or MCI(s) which have higher lattice enthalpy.
Solubility: The solubility of an ionic compound in water (or any other solvent) depends on
La standard Gibbs free energy change (AG°) of the process
MX(S) - M*(aq) + X(aq).
The standard free energy change for the dissolution of the salt, AG°, is related to the solubility
product K, by the relation AG = -RT In K,.
The process of dissolution may be deait with conveniently by aBorn-Haber type cycle
involving the following steps.
Process Enthalpy change
) Disruption of 1 mol of solid crystal into Lattice enthaipy AH,
gaseous ions: MX(s) ’ M*(g) + X(g) (energy is required).
Gi) Conversion of the gaseous cations and anions Hydration enthalpy:
into hydrated ions in solution: AHydration of M*(g) + X(g)
M(g) + X (g) ’ M*(aq) + X (aq) (energy in released).
The overall enthalpy of solutions, AH, (heat of solution at infinite dilution) is clearly the sum
of these enthalpy changes. For a salt of known solubility product, we can calculate AG; and
obtain AS° (entropy change for dissolution) through the relation AG° = AH - TAS.
Relative magnitudes of lattice enthalpy of the crystal and heats of hydration of the ions
determine the magnitude of heat of solution--it may be positive or negative. For very soluble
substances it is often (but not always) negative, corresponding to an exothermic process.
Substances with apositive heat of solution may stillhave an overallnegative free energy of
dissolution by predominance of the entropy term. As the ordered arrangement of the ions in
the crystal latice is destroyed, there is a large increase in entropy. However. orientation of the
randomly distributed solvent molecules around the ions decreases the entropy of the system to
some extent. The overal entropy factor (TAS) drives the process of dissolution; the work to
pullthe ions apart is done at the cost of the intemal energy of the system (adiabatic condition),
and the solution cools. If the enthaply of solution is sufficiently positive, the entropy term
cannotoutweigh this and the compound does not dissolve (e.g.. BaSO,. CaF, etc.).
For an ion of charge Ze and radius r, the free energy of hydration (solvation) may be
expressed as

AGhydration
where [ is the permittivity of free space and k, is the relative permittivity (dielectric constant)
of water (or solven). This shows that hydration (solvation) energy is greater in magnitude for
Small ions and high charge and in a solvent of high dielectric constant (Table 8.12). AIl these
tactors therefore favour issolution of an ionic substance. Further. the attractive force between
the ions in a solvent of high dielectric constant will also be smaller.
 366 /GENERAL AND INORGANIC CHEMISTRY (PART-)
However, the equation gives only approximate results as the bulk relative permittivity of
the solvent in the vicinity of an ion becomes different and the crystal radiusof an ion does no
represent its radius in solution. Nevertheless it has been possible to provide comparison be.
tween different ions and compilation of AG, AH° and AS° values for hydration of different
ions (Table 8.12). The dependence of AGRdatien on size andcharge of the ions is also reflected
in the values for AH° and AS°. The entropy contribution (TAS°; AS° values in Joules) is always
much less than the enthalpy term (kJ), specially at ordinary temperature. So useful corelations
between solubility and enthalpy of hydration have been made possible.
Table 8.12
AG, AH (J mot)and As (J motl) of hydration (kJ mo) for some ions at 298K.
AHO AS AG AH AS AGO
-1120 -121 -1084 Mg2+ -1980 -293 -1895
Lit -544 -134 -506 Ca2+ -1650 -238 -1582
Nat 435 -100 -406 Ba2+ -1365 -188 -1310
K+ -352 -67 -330 AJ3+ 4750 -506 4600
Rb+ -326 -54 -310 F -473 -142 -432
Cs+ -293 -50 -276 CI -339 -84 -314
-260 -46 -247
The hydration enthalpy of a salt of the type MX may be expressed as the sumn of
contri
butions by individual ions:

AH hyd k, kyi Constants; r, r:radii of cation and anion.

For successful dissolution of the salt, this hydration
enthalpy should overcome the lattice
enthalpy; the latter may also be expressed as a function of the sum of ion-radii:
AH; = k (k =a constant).
In a series of related compounds, the variation of AHv
and AH, would be different as the
two quantities will respond differently to the
variation of r, orr along the series. If for
example, r, << r, the contribution of the anion to the hydration
total AHnv of the ion-pair will be dominated by the enthalpy will be small; the
cation alone. In a series of salts of a large
anion, the hydration enthalpy will gradually decrease in magnitude with
(e.g., LiCIO,, NaClO, KCIO4 or LiI ... CsI). But the
increasing cation size
to the sum (r, + r). Since r_ lattice enthalpy inversely proportional
is
>>r, the sum will not change as , increases.
Consequently the lattice enthalpy will not decrease as fast as the significantly
hydration enthalpy decreases
with increasing cation size. The more
decrease in solubility along the series: quickly diminishing hydration enthalpy results
LiCIO, > NaCl0, >
LiI > Nal
KCIO,
KI CsI
MgSO, > CaSO, SrSO, > BaSO,
 8.3.3 PROPERTIES OF IONIC
alkali
COMPOUNDS / 3o7
Some data on metal halides may be found in
exafluorophosphates, chapter 18. Similar arguments apply to
chloridoplatinates(IV) hexanitrocobaltate(IIl).
otK,{Co(NO)]is used to detect potassium ion and in solution in qualitative The low solubility
analysis.
With asmall anion, the lattice enthalpy decreases more rapidly along aseries of salts with
cation size and
solubility
thesolubilitytrend when r, r, Thisincreases.
inCTeaSing In general, the lattice
is reflected in enthalpy
the trend of solubility term
among thedetermines
fluorides
andhydroxides - LiF < NaF <.. CsF and Mg(OH), < Ca(OH),... Ba(OH),- Barium hydroxide
solution is used as a titrant
in
lavever, variation of solubility mayalkalimetry.
baryta)
have quite other different origin, too. The solubility
damong the silver halides (AgF> AgCl > AgBr > Ag) is
an example (see later).
Polarization of ions
The properties of 10nic compounds expected from purely ionic composition of the solid is
ally an idealization. The electron probability densities ("electron clouds") of
ons do interact with one another to impart some covalent character to an neighbouring
ionic compound. As
aConsequence, 1ons are partly deformed or polarized from their ideal spherical shape, their
lectrostatic interaction is weakened and the lattice enthalpy of the compound is actually low
ered. With increasing polarization, the charge clouds of neighbouring cations and anions would
ultimately tend to overlap with one another as in a covalent compound. The extent of polar
ization is thus a measure of the tendency of the system to attain covalent character.
This trend of attaining covalent character by ionic compounds as a consequence of polar
zation may be generalized in terms of Fajan's rules (1924). According to these rules, (orig
inally stated in terms of atomic volume), an ion will be formed most easily when
(i) the electronic structure of the ion is stable,
(ii) the charge on the ion is small,
and (ii) a small atom forms the anion or a large atom forms the cation.
Conversely, if these conditions are not fulfilled, covalent character will develop in the
Ompounds concerned. Thus, increased covalence is favoured by
(i) high charge on the ions,
(ii) small size of the cation and large size of the anion
aid, (ii) cations with 18-electronstructures (i.e., 'non-inert gas' type; e.g., Cut).
e significance of these rules is not difficult to understand. High charge and small size of
cation imparts greater polarizing power1to it. Similarly, the electron cloud of an anion is more
it use when its charge or size is large. This makes the anion easily polarizable.
The Corresponding increase of covalent character is reflected in the decreasing melting
oint of the Compounds as illustrated in the table belovw. However, other factors like
packing
COntributes to the melting point.