Ch 5 Energetics

5.1 Exothermic and endothermic reactions

5. 1. 1. Define the terms exothermic reaction, endothermic reaction and standard
enthalpy change of combustion.
& 5. 1. 2. State that combustion and neutralization are exothermic processes.
Energy: a measure of the ability to do work
Work: moving an object against an opposing force.
1

Joule: a unit of energy and work. 1 = 1

Heat: a form of energy transferred as a result of temperature difference and produces an increase in
disorder in how particles behave
A system can either be closed (only exchange of energy, but not of matter with surroundings) or open
(matter and energy exchange).

In chemical reactions, heat is exchanged between the system and the surroundings.
Enthalpy refers to the heat content of a substance. The enthalpy change (H) is often measured and
calculated, because the absolute value of enthalpy cannot be determined.
Reactions that release more heat than they absorb (they heat up the surroundings) are called exothermic.
As the system loses energy, its H is negative.
Reactions that absorb more heat than they release (they cool down the surroundings) are called
endothermic. As the system gains energy, its H is positive.

Standard enthalpy change of combustion refers to the energy change associated with the combustion of
1 mol of a substance in standard conditions. Combustion is an exothermic process.

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Standard enthalpy change of neutralization refers to the

energy change associated with the production of 1 mol of water
in a neutralization reaction. Neutralization is an exothermic
process.

Standard conditions:
temperature: 298K = 25C
pressure: 100kPa

5. 1. 3. Apply the relationship between temperature change, enthalpy change and

the classification of a reaction as endothermic and exothermic.
Common mistakes:
1) When recalculating between change in
temperature and heat change, you will often
be given the temperature or heat change of
water or air in which the reaction takes
place. You must remember that this is the
surroundings and not the system the heat
change of the system will have the opposite
sign!

Heat change (Q) refers to the heat energy change

of a system.
=

[] = [] [ ] []
Specific heat capacity (c) or (cp) is the heat needed
to increase the temperature of unit ass of a
material by 1K. Remember, that cwater=4.18Jg-1K-1.

When they ask: How much heat is

released? your answer should mention
Qsystem.

[ 1 ] =

[]
[]

When they ask: How much heat is

absorbed? your answer should mention
Qsurroundings.
2) H is usually given to you in kJmol-1, while
Q in J. Remember, that you need to
recalculate between J and kJ.

type of
reaction
exothermic
endothermic

Qsystem

Qsurroundings

negative
positive

negative
positive

positive
negative

positive
negative

5. 1. 4. Deduce, from an enthalpy level diagram, the relative stabilities of reactants

and products and the sign of enthalpy change for the reaction.
Substances are most stable in a state of lowest energy. Therefore, chemicals react in a way that reduces
their enthalpy.
Products of exothermic reactions are more stable than the reactants.

Reactants of endothermic reactions are more stable than the products.

This does not mean that endothermic reactions cannot occur spontaneously!

5.2 Calculation of enthalpy changes

5. 2. 1. Calculate the heat energy change when the temperature of a pure substance
is changed.
see 5. 1. 3.

5. 2. 2. Design suitable experimental procedures for measuring the heat energy

changes of reactions
& 5. 2. 3. Calculate the enthalpy change of a reaction using experimental data.
2

A device used for measuring heat energy changes is called a

calorimeter. It is an insulated vessel.
You will measure the temperature change either of the reaction
mixture or of the surroundings. Remember, that in neutralization,
water is produced, therefore you are measuring the temperature
change of water => of the surroundings!
After having determined t, recalculate using the formulae in 5.
1. 3.

5. 2. 4. Evaluate the results of experiments to determine enthalpy changes.

Work with the definitions in combustion, recalculate for 1 mol of fuel. In neutralization, recalculate for 1
mol of water produced.
When comparing your values with the tabulated values, you must remember that you have not
performed your experiment in standard conditions. In combustion, for instance, you heated up the
system externally.
Note that the tabulated value of enthalpy change of neutralization considers only strong acids and alkali
if you are working with vinegar, for instance, your results will be completely different!

5.3 Hesss law

5. 3. 1. Determine the enthalpy change of a reaction that is the sum of two or three
reactions with known enthalpy changes.
Hesss law states that the enthalpy change for any chemical reaction is independent of the route,
provided the starting conditions and final conditions, and reactants and products, are the same.
2

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This means that for the following reaction:

3

= 1 + 2
It is important that you follow the direction of the lines
you draw! Let us look at an example:

Common mistakes:
1) Always follow the lines you draw. If you
see a combustion going the opposite way
(oxygen is formed, rather than used), invert
the sign of the enthalpy too!
2) Work with the definition. If your reaction
involves stoichiometric coefficients, adjust
your calculation. For example, if you were to
produce 2CO, you will need to multiply the
enthalpy change of combustion by 2 as well.
3) If you are given seemingly less information
than you need, think about the last process
you might need. In our reaction, we are not
given Hoc of oxygen. However, O2+O2->2O2
and no energy change is involved -> use a
zero.

As you can see, it is necessary to break down the reaction into partial reactions using the information you
were given. Remember to change the signs if the process goes the opposite way than the data you were
given.

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5.4 Bond enthalpies

5. 4. 1. Define the term average bond enthalpy.
The standard bond enthalpy is the energy needed to break one mole of bonds in gaseous molecules
under standard conditions.
The enthalpy of the same bond is different in different environments, which is why the concept of
average bond enthalpy was introduced.
The same energy is given off when a bond is broken as is absorbed when a bond is made (and so,
remember the opposite sign!)
Multiple (double and triple) bonds usually have a higher bond enthalpy than single bonds.

5. 4. 2. Explain, in terms of average bond enthalpies, why some reactions are

exothermic and others are endothermic.
A chemical reaction can be broken up into two parts. In the first half, bonds are broken, in the second
half, bonds are made.
The activation energy is equivalent to the breaking of all bonds and thus the sum of all bond enthalpies of
the original molecules. Also:

=
*(Substracting the breaking of bonds is the same as adding the making of bonds)

It can thus be deduced that reactions in which the sum of bond enthalpies of products is greater than the
sum of bond enthalpies of reactants are exothermic!
It can thus be deduced that reactions in which the sum of bond enthalpies of reactants is greater than the
sum of bond enthalpies of products are endothermic!
Reactions will be spontaneous if the enthalpy change of breaking bonds in reactants can be provided by
heat in the surrounding will occur spontaneously at those conditions. (Note: this is almost true, yet a simplification, the
energy could also be provided by a change in entropy. You can use it at SL, at HL you need to take entropy into account)

When calculating H of a reaction using enthalpies, you must remember to multiply the bond enthalpies
by the occurrences of that type of a bond. Also, you must remember to change the sign if a bond is made,
rather than broken.

HL: (Novy PORG, we did this in SL!!!)

15.1 Standard enthalpy changes of reaction
15. 1. 1. Define and apply the terms standard state, standard enthalpy change of
formation and standard enthalpy change of combustion.
Standard enthalpy change of formation refers to the energy change associated with the formation of 1
mol of a substance from all its constituent elements in their standard state under standard conditions.

The standard state of a substance is the pure form of the substance under standard conditions.
For rest, see 5. 1. 1.

15. 1. 2. Determine the enthalpy change of a reaction using standard enthalpy

changes of formation and combustion.
Done in the same way as 5. 3. 1. => apply Hesss law.
Example:

(Novy PORG, HL for us too, starting now)

15.2 Born-Haber cycle

15. 2. 1. Define and apply the terms lattice enthalpy and electron affinity.
Lattice enthalpy is the energy change associated with the separation of 1 mol of a solid ionic substance
into gaseous ions under standard conditions.

First electron affinity is the energy change associated with the attraction of 1 mol of electrons by 1 mol of
gaseous atoms.
Enthalpy of atomization is the energy change associated with the formation of 1 mol of gaseous atoms
from the element in standard state.

15. 2. 2. Explain how the relative sizes and the charges of ions affect the lattice
enthalpies of different ionic compounds.
The exchange of electrons required in formation of an ionic bond in itself is endothermic. However, ionic
lattice formation is a very exothermic process and therefore on the whole, formation of a salt is
exothermic.
To answer this assessment statement, we must remember electron affinity and ionization energy and
how these are affected by size and charge. Please, refer back to my notes on Periodicity

15. 2. 3. Construct a Born-Haber cycle for Group 1 and 2 oxides and chlorides and
use it to calculate an enthalpy change.
A Born-Haber cycle is a diagram applying Hesss law. It shows all the various energy changes and can be
used to work out any reaction described in it.
4

Since the lattice enthalpy cannot be directly

measured, it must be calculated using the
Born-Haber cycle.

15. 2. 4. Discuss the difference

between theoretical and
experimental lattice enthalpy
values of ionic compounds in terms
of their covalent character.
The theoretical value of lattice enthalpy can be calculated based on the ionic model. The ionic model
assumes:

perfectly spherical ions

only electrostatic forces play a role

+ )

+
(

+
Where Knm is a constant which depends on the geometry of a lattice and (
+ ) is the sum of the
ionic radii of both ions. Notice that this means that lattice enthalpy is greater for ions with smaller ionic
radii.
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However, there are differences between the lattice enthalpy

calculated from the Born-Haber cycle and using this equation. This is
because of the assumptions of the ionic model. In reality, not all ions
are perfectly spherical. A polarization may occur.
5

The picture demonstrates this. Since Al2O3 will deviate from the
assumptions of the models most, the % error will be the greatest.
The % error can also be used to determine the covalent character of
an ionic compound it will be greatest for the most covalent ones.
This is because a covalent bond can be considered an extreme case
polarization.

15.3 Entropy will be completed when covered in our school

15. 3. 1. State and explain the fact ors that increase the entropy in a system

15. 3. 2. Predict whether the entropy change for a given reaction or process is
positive or negative.

15. 3. 3. Calculate the standard entropy change for a reaction using standard
entropy values.

15.4 Spontaneity
15. 4. 1. Predict whether a reaction or process will be spontaneous using the sign
of G o .

15. 4. 2. Calculate G o for a reaction using the equation G o = H o - TS o and by

using values of the standard free energy change of formation G o f .

15. 4. 3. Predict the effect of a change in temperature on the spontaneity of a

reaction, using standard entropy and en thalpy changes and the equation G o = H o
- TS o .

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