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Enthalpy changes
The enthalpy change for a process
is the heat energy exchanged with
the surroundings at constant
pressure.
Enthalpy change is given the symbol H.
The units are kJ mol1.
Enthalpy changes are frequently
measured under standard conditions,
i.e. 298 K and 100 kPa. If an enthalpy
change is measured under standard
conditions, the symbol is used in
superscript, H.
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Enthalpy changes

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Examples of enthalpy changes

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Bond enthalpies
When a chemical reaction takes place, bonds are broken in
the reactants and bonds are formed in the products. Breaking
bonds is an endothermic process. Making bonds is an
exothermic process.
The enthalpy change for a reaction can be calculated by
working out the enthalpy changes for bonds made and bonds
broken during the reaction using mean bond enthalpies.
The mean bond enthalpy is the average (mean)
bond dissociation enthalpy for a particular bond in
a range of different compounds.
Precisely, it is the average enthalpy change for
breaking 1 mole of a particular bond in a range of
different compounds in the gas phase.
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Calculations using bond enthalpies

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What is a BornHaber cycle?

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Constructing a BornHaber cycle

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BornHaber cycle for MgCl2

Mg2+(g) + 2Cl(g) + 2e
Hi(2nd) (Mg) = +1450

Hi(1st) (Mg) = +736

2 Ha (Cl) =
2 (+121)
Ha (Mg) = +150

Mg+(g) + 2Cl(g) + e

2 Hea (Cl) =
2 (364)

Mg(g) + 2Cl(g)

Mg2+(g) + 2Cl(g)

Mg(g) + Cl2(g)
Mg(s) + Cl2(g)
Hf (MgCl2)

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Hl (MgCl2) = 2493

MgCl2(s)
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Can you construct a BornHaber cycle?

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BornHaber cycle questions

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Lattice formation enthalpies

When an ionic lattice is formed, the oppositely charged ions
are attracted to each other. The stronger the attraction, the
higher the lattice formation enthalpy.
Two factors increase the attraction and therefore the lattice
formation enthalpy:

high charge

O2

N3

increasing lattice formation enthalpy

small size.
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K+

Na+

Li+
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Polarization and lattice enthalpy

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Fill in the missing words: lattice enthalpy

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Enthalpies of solution and hydration

The standard enthalpy of solution
(Hsol) is the enthalpy change
when one mole of an ionic
compound is dissolved in water to
produce aqueous ions.
NaCl(s)

Na+(aq) + Cl(aq)

The standard enthalpy of hydration (Hhyd) is the

enthalpy change when one mole of gaseous ions is
converted to one mole of aqueous ions.
Na+(g)

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Na+(aq)

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Calculating enthalpies of solution

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Enthalpy of solution calculations

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Factors affecting enthalpy of hydration

The size of the enthalpy of hydration depends on:

The size of the ion. The smaller the ion, the larger the
enthalpy of hydration.
Ion

Hhyd (kJ mol1)

Ion

Hhyd (kJ mol1)

Li+
Na+

519
406

F
Cl

506
364

K+

322

Br

335

increasing size

The charge on the ion. The larger the charge on the ion,
the larger the enthalpy of hydration.
Ion

Hhyd (kJ mol1)

Ion

Hhyd (kJ mol1)

Fe2+

1950

Fe3+

4430

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What is a spontaneous reaction?

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Entropy
Entropy is a measure of disorder, and is given the
symbol S. The units of S are: J K1 mol1.

ordered

disordered

regular arrangement
of particles

random arrangement
of particles

low entropy

high entropy

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Entropy change for reactions

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Predicting entropy changes

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Calculating entropy changes

Standard entropy changes for any chemical reaction or
physical change can be calculated using the following simple
expression:
S = Sproducts Sreactants
Remember the following points:

the units of entropy, S, are J K1 mol1

entropies of elements are not zero like Hf values, so they

should be included in calculations.
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Calculating entropy changes

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Entropy change calculations

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Entropy changes in the surroundings

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Entropy changes in the surroundings

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Gibbs free energy

Whether a reaction is spontaneous depends on:

the entropy change of the system

the enthalpy change of the system

the temperature.

The change in a quantity called the Gibbs free energy

provides a measure of whether a reaction is spontaneous.
The Gibbs free energy change is given the symbol G and
can be calculated for a reaction using the expression:
G = H TS

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A reaction will be spontaneous if G <

0.

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How to calculate G

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Calculating G

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Feasibility of reactions
Even if G is positive at room temperature, there may be a
higher temperature at which a reaction becomes feasible.
G = H TS
If S is positive, there may be a point at which TS is big
enough to outweigh the enthalpy factor.
H

As temp. increases

positive

positive

makes TS > H

negative positive

makes G more negative

positive negative no effect: G always positive

negative negative unlikely to make TS > H
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Feasible?
yes, above a
certain temp.
always
never
usually
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Finding the temperature

Consider the reduction of aluminium oxide with carbon:
Al2O3(s) + 3C(s)
H = +1336 kJ mol1

2Al(s) + 3CO(g)
S = +581 J K1 mol1

As both H and S are positive, G will become negative if

TS > H.
The temperature at which this reaction becomes feasible
can be calculated. This will be when G = 0.
If G = 0, then T = H / S
T = 1336 / (581/1000)
T = 2299 K
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When is a reaction feasible?

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Solubility
In the same way that reactions are only feasible if G < 0, a
substance will be soluble in water at a specific temperature
if Gsol < 0.
Gsol = Hsol TSsol
Hsol

Ssol

positive

positive

G / feasibility
feasible if T is large enough to make
G negative

negative positive

always feasible

positive negative

never feasible
usually feasible (T is unlikely to be
large enough to make G positive)

negative negative

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Thermodynamics vs. kinetics

Just because a reaction is spontaneous does not mean that it
appears to happen. It may be that the reaction is so slow or has
such a high activation energy that it is not generally observed.
Consider the reaction involving the combustion of carbon:
C(s) + O2(g)
H = 394 kJ mol1

CO2(g)
S = +3 J K1 mol1

This reaction has a negative value for G, so is feasible, but a

piece of carbon does not spontaneously burn if left on the
table. Energy would need to be put in for the reaction to begin.
A reaction that is thermodynamically feasible is not necessarily
kinetically feasible.
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Glossary

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Whats the keyword?

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Multiple-choice quiz

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