4.

1: Energetics II
Definitions
Enthalpy of atomisation is the enthalpy change when one mole of gaseous
atoms is formed from the original element in its most stable state at 1atm
pressure and 298K.
E.g. Na
(s)
 Na
(g)
Enthalpy of hydration is the enthalpy change when one mole of gaseous ions is
dissoled in e!cess water to form an infinitely dilute solution.
E.g. "a
2#
(g)
# a$  "a
2#
(a$)
Lattice energy is the e!othermic enthalpy change when one mole of ionic solid
is formed from its constituent ions.
E.g. %
#
(g)
# &
'
(g)
 %
#
&
'
(s)
Born-Haber cycles
( )orn'*aber cycle is a *ess+s law cycle in which,
' the direct change is from elements to a solid ionic compound
' the indirect route inoles atomising the elements- ionising the atoms and
bringing the gaseous ions together to form the solid ionic compound.
Application of Born-Haber cycles
)orn'*aber cycles can be used to determine the electron affinity of an atom or
the lattice enthalpy of an ionic solid.
actors affecting lattice energy
Ionic charge
.he greater the charge- the stronger the force between the positie and
negatie ions. .herefore- the lattice energy is more e!othermic.
!"m of the ionic radii
.he smaller the sum of the ionic radii- the stronger is the force between the
positie and negatie ions. .herefore the lattice energy is larger.
/attice energy alues calculated using the )orn'*aber cycle are always more
e#othermic than alues calculated using the purely ionic model. .he lattice
energy also depends upon the e!tent to which the anion is polarised by the
cation- which causes a slight degree of coalency. /arger anions are more
easily polarised. 0maller- highly charged cations are powerful polarising agents.
1f a significant degree of polarisation occurs- the e!perimental lattice energy
obtained from a )orn'*aber cycle will be greater than that calculated from the
purely ionic model.
!ol"bility and trends
( solute is soluble in a gien solent if the energy re$uired to separate the
solute particles is compensated for by the energy released in the attractions
between the solute particles and the solent molecules.
Enthalpy of sol"tion of ionic s"bstances
2sing *ess+s law- we can show that.
Enthalpy of sol"tion $ -lattice energy % s"m of hydration enthalpies of ions
3rom this e$uation- we can see that if the e!othermic hydration enthalpies
compensate for the endothermic brea4down of the lattice ('lattice energy)-
enthalpy of solution will be negatie- i.e. e!othermic- and the ionic solid will
dissole in the solent.
!ol"bility of gro"p & hydro#ides
' 0olubility increases down the group.
' .he charge on the ions does not change.
' .he radius of the cation increases as the group is descended. .he
hydro!ide ion has a radius similar to the group 2 cations- so the sum of
the ionic radii increases significantly down the group. .his means that
the lattice energy decreases sharply down the group.
' .he hydration enthalpy of the cation is independent of the anion and
also decreases sharply as the group is descended.
' .he lattice energy decreases slightly more than the hydration
enthalpies- and so enthalpy of solution becomes more e!othermic.
' *ence the solubility of the group 2 hydro!ides increases down the group.
!ol"bility of gro"p & s"lphates
' 0olubility decreases down the group.
' .he charge on the ions does not change.
' .he radius of the cation increases as the group is descended. .he
sulphate ion has a ery large radius compared to the group 2 cations- so
the sum of the ionic radii is hardly affected. .his means that the lattice
energy decreases slightly down the group.
' .he hydration enthalpy of the cation is independent of the anion and
also decreases sharply as the group is descended.
' .he hydration enthalpies of the ions decreases more than the lattice
energy of the ionic compound- and so enthalpy of solution becomes
more endothermic.
' *ence the solubility of the group 2 sulphates decreases down the group.

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