TOPIC 15

ENERGETICS/THERMOCHEMISTRY

15.1
ENERGY CYCLES
 ESSENTIAL IDEA
The concept of the energy change in a
single step reaction being equivalent
to the summation of smaller steps can
be applied to changes involving ionic
compounds.
NATURE OF SCIENCE (3.2)
Making quantitative measurements with replicates
to ensure reliability – energy cycles allow for the
calculation of values that cannot be determined
directly.
 UNDERSTANDING/KEY IDEA
15.1.A
Representative equations
(e.g. M+(g) → M+(aq)) can be used
for enthalpy/energy of
hydration, ionization,
atomization, electron affinity,
lattice, covalent bond and
solution.
 GUIDANCE
The following enthalpy/energy
terms should be covered:
ionization, atomization,
electron affinity, lattice,
covalent bond, hydration and
solution.
• The lattice enthalpy (ΔHlatº ) is defined as
the change in enthalpy that occurs when
one mole of a solid ionic compound is
separated into its gaseous ions under
standard conditions.
• Electron affinity (ΔHeaº) is the enthalpy
change when one mole of gaseous atoms
attracts one mole of electrons.
• Enthalpy change of atomization (ΔHatomº)
is the heat change when one mole of
gaseous atoms are formed from the
element in its standard state.
• The bond enthalpy for a covalent bond
(E) or (ΔHº) is defined as the energy
needed to break one mole of bonds in
gaseous molecules under standard
conditions.
• Ionization energy (ΔHieº) is the energy
required to remove a mole of electrons
from a mole of gaseous atoms to form a
mole of cations in the gaseous state.
• ΔHatomº = M
(s) → M(g)

• E = bond enthalpy (covalent bond)

• ΔHieº = M(g) → M+(g) + e-
• ΔHeaº = X(g) + e-→ M-(g)
• ΔHlatº = MX(S) → M+(g) + X-(g)
• ΔHsolº = MX(S) → M+(aq) + X-(aq)
• ΔHhydº = M+(g) → M+(aq)
 APPLICATION/SKILLS

Be able to construct Born-

Haber cycles for group 1 and 2
oxides and chlorides.
 APPLICATION/SKILLS

Be able to calculate enthalpy

changes from Born-Haber or
dissolution energy cycles.
Born-Haber Cycle

• This is an energy cycle based on

Hess’s Law.
• This is used because lattice
energies cannot be determined
directly.
• The formation of an ionic
compound from its elements takes
place in a number of steps.
 Formation of NaCl
Na(s) + ½ Cl2(g) → NaCl(s) ΔHf˚ = -411 kJ/mol

• Step 1: Atomize sodium ΔHatom˚ = +107

Na(s) →Na(g)
• Step 2: Form one chlorine gas ½E(Cl-Cl) = ½(+243)
break the Cl2 bond
½ Cl2(g) → Cl(g) E is bond enthalpy given in table
• Step 3: Remove one e- from the ΔHi˚= +496
gaseous sodium atom
Na(g) → Na+(g) + e-
• Step 4: One e- is added to the ΔHe˚= -349
• gaseous chlorine atom
Cl(g) + e- → Cl-(g)
• Step 5: The gaseous ions form ΔHlat˚ = ?
• one mole of solid NaCl.
• Na+(g) + Cl- (g)→ NaCl (s)
 Na+(g) + e- + Cl-(g)

ΔHe˚(Cl)= -349

ΔHi˚(Na)= +496
Na+(g) + Cl- (g)

Na(g) + Cl(g)

Na(g) +½Cl2(g) ½E(Cl-Cl) = ½(+243)

Na(s) + ½Cl2(g)
ΔHatom˚ = +107 ΔHlat˚(NaCl) = ?

ΔHf˚ (NaCl)= -411 kJ/mol

From Table 10 NaCl(s)

• ΔHf˚ (NaCl)= ΔHatom˚+½E(Cl-Cl) + ΔHi˚(Na) + ΔHe˚(Cl) - ΔHlat˚(NaCl)

• -411 = 107 + ½ (243) + 496 + (-349) - ΔHlat˚(NaCl)
• ΔHlat˚(NaCl) = +786.5kJ/mol
OXYGEN EXCEPTION
• Note that when oxygen is used in an ionic
compound that there is a different treatment
for (ΔHeaº).
• If your cation is a 2+ ion, you will be using 2
ionization energies. The 2nd ionization energy
will have to be given to you in the problem.
The 1st can be found in the data booklet.
• Oxygen will have an exothermic 1st (ΔHeaº)
and an endothermic 2nd (ΔHeaº).
• The 2nd is endothermic because you are trying to
add an electron to a negatively charged species
and you have to overcome the neg-neg repulsions.
 APPLICATION/SKILLS

Be able to relate size and

charge of ions to lattice and
hydration enthalpies.
• Two things affect lattice
enthalpy:
• The higher the charge – the
stronger the lattice enthalpy.
• The smaller the ion – the stronger
the lattice enthalpy.
 UNDERSTANDING/KEY IDEA
15.1.B
Enthalpy of solution, hydration
enthalpy and lattice enthalpy
are related in an energy cycle.
• The enthalpy change of solution (ΔHsolº ) is
defined as the change in enthalpy that occurs
when one mole of a solute is dissolved in a
solvent to form aqueous ions in an infinitely
dilute solution under standard conditions.
• Dissolving an ionic cmpd to make aq ions.
• The enthalpy change of hydration (ΔHhydº ) is
defined as the change in enthalpy that occurs
when one mole of gaseous ions is dissolved to
form an infinitely dilute solution of one mole of
aqueous ions under standard conditions.
• Refers to the individual ions
 INFINITELY DILUTE
SOLUTIONS
• The interaction between the solute and
the solvent water molecules depends upon
the concentration of the solution.
• The enthalpy of solution strictly refers to
the ideal situation of infinite dilution.
• To obtain this value, measure the enthalpy
changes for solutions with increasing
volumes of water until a limit is reached.
SOLUTIONS

• Ionic compounds are crystal

lattices.
• They readily dissolve in water.
• The ions are strongly attracted to
the polar water molecule.
• The partial positive charge on the
hydrogen attracts the negative
ions.
• The partial negative charge on the
oxygen in the water molecule
attracts the positive ions.
• Ions separated from a crystal lattice
in this manner become surrounded
by water molecules and are said to
be hydrated.
• The strength of interaction between
the polar water molecules and the
separated ions is given by the
hydration enthalpy.
• The enthalpy of hydration of
individual ions cannot be measured
directly because both types of ions
are present and the contribution of
each ion cannot be disentangled.
• The problem is resolved by
measuring the enthalpy of hydration
of the H+ ion and then combining
this value with the hydration
enthalpy of different compounds to
obtain values for individual ions.
• Remember the enthalpy of
hydration of an ion is the enthalpy
change that occurs when one
mole of gaseous ions is dissolved
to form an infinitely dilute solution
of one mole of aqueous ions.
• There is a force of attraction
between the ions and the polar
water molecules so the process is
exothermic and the value for ΔHhydº
is negative.
• The ΔHhydº becomes less
exothermic as ionic radius
increases (down a group).
• The force of attraction is less as
the distance between the water
molecule and the ions increases.
• The ΔHhydº becomes more
exothermic across a period
because charges increase and
size decreases.
 APPLICATION/SKILLS

Be able to construct energy

cycles from hydration, lattice
and solution enthalpy. For
example dissolution of solid
NaOH or NH4Cl in water.
 GUIDANCE
Values for lattice enthalpies
(section 18), enthalpies of
aqueous solutions (section 19),
and enthalpies of hydration
(section 20) are given in the
data booklet.
EXAMPLE PROBLEM

• Use an energy cycle to calculate

the enthalpy of solution of NaCl
from data sections 18 and 20 in
the IB data booklet.
• Compare your value with the value
in section 19 of the data booklet and
comment on the disagreement
between the 2 values.
The enthalpy of solution is solved by adding the lattice
enthalpy of the ionic solid (section 18) and the separate
hydration enthalpies of the ions (found in section 20 of the
IB data booklet).

ΔHsolº = ΔHlatº(NaCl) + ΔHhydº(Na+) + ΔHhydº (Cl-)

= +790 – 424 – 359 kJ/mol
= +7 kJ/mol
The value obtained in section 19 is +3.88 kJ/mol.

The % inaccuracy = (7-3.88)/3.88 x 100 = 80%

The disagreement between the two values illustrates a

general problem when a small numerical value is calculated
from the difference of two large numerical values.
Citations
Brown, Catrin, and Mike Ford. Higher Level
Chemistry. 2nd ed. N.p.: Pearson
Baccalaureate, 2014. Print.

Most of the information found in this power

point comes directly from this textbook.

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complement the Higher Level Chemistry
textbook by Catrin and Brown and is used for
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