EntHaLpy

 heat content (denoted as H or ΔH) is a

quotient or description of
thermodynamic potential of a system, which
can be used to calculate the "useful" work
obtainable from a closed
thermodynamic system under constant
pressure.
It is often calculated as a differential sum,
describing the changes within exo- and endo
thermic reactions, which minimize at
equilibrium.
 EntHaLpy
H = U + PV

has units of energy, but it doesn’t necessarily

have a direct physical interpretation as a
quantity of heat

itis just a defined variable that often simplifies

the calculations in the solution of practical
thermodynamic problems.
 EntHaLpy of SoLution
 The amount of heat that is absorbed or
released when a solute is dissolved in a solvent

 ΔHsoln is negative when the solution process

releases heat
 ΔHsoln is a positive value when the solution
absorbs heat
 ΔHsoln = 0 in the case where no heat is
absorbed or released
 EntHaLpy of SoLution
The magnitude of ΔHsoln provides information
about relative intermolecular forces of solute,
solvent, and solution. When ΔHsoln = 0, the
solution is referred to as an ideal solution.

The enthalpy of solution is the enthalpy

associated with the process when a process
enters solution. There can be different types of
enthalpy of solution, the most common being:
 EntHaLpy of SoLution
(a) The integral enthalpy of solution - the
enthalpy change when one mole of solute
dissolves in a large excess of pure solvent.

(b) The differential enthalpy of solution - the

enthalpy change when one mole of solute
dissolves in a large amount of solution.

(c) The enthalpy of hydration is reserved for

the special case when the solvent is water.
 EntHaLpy of Hydration

 Enthalpies of hydration are always negative.

 They depend on the charge and size of an ion.

 They become more negative when ionic charge

increases or when ionic radius decreases. When
we deal with solvents other than water we use
the term enthalpy of solvation, ΔHsolv
 Lattice EntHaLpy
 The heat evolved when one mole of a crystalline ionic
compound forms from its gaseous ions, measured under
standard conditions.

The magnitude of the lattice enthalpy depends on how

closely the ions pack together in the crystal structure.

The more closely they pack the more exothermic the

lattice enthalpy.

The higher the charge on the ions and the smaller their
size, the more closely they will pack in the crystal
structure.
 Trends in Lattice EntHaLpy
Down group I lattice enthalpies become less
exothermic. (The same applies down group II)

 Down group VII the lattice enthalpies become

less exothermic, as the heat of formation
becomes less exothermic and as partly as the
enthalpy of atomization becomes less
endothermic, due to the larger size of the atoms,
and therefore weaker bonds between them as
elements.
Answers to Questions
How is the heat solution of CaCl2 affected by:
a) number of moles of CaCl2? b) number of
moles of H2O? Explain the significance.

 as mole of calcium chloride increases, heat

of solution increases
 as moles of water increases, heat of
solution also decreases
Plot cation radius against lattice enthalpy for CaCl2,
NaCl, and KCl. Explain the observed trend.
 The larger the cation
radius, the smaller the
lattice enthalpy (inversely
proportional).
Explain the significance of the partial molar
heats of solution of solute and solvent.

 The dissolution process involves both bond

breaking and bond formation; one may consider
the breaking of solute-solvent bonds that
contribute to a decrease in energy, and the
formation of solute-solvent bonds that
contribute to an increase in energy.
This energy is computed on a per molar basis,
and because the result in dissolution process is
a solute-solvent mixture, one must consider the
partial molar heats of solution of solute and
solvent in calculating the enthalpy of solution.
Plot anion radius against lattice enthalpy for
KCl, Kbr, and KI. Explain the observed trend.
Lattice enthalpy is
dependent on the reciprocal of
anion radius.