ENERGETICS

Specific Objectives
 State that chemical reactions take place through energy
changes

 State that energy changes occur in chemical reactions

associated with the making and breaking of bonds

 Explain the differences between exothermic and

endothermic reactions using energy profile diagrams

 Explain the term ‘bond energy’

Specific Objectives
 Explain how bond energy data may be used to show the
relationship between strength of covalent bonds and
reactivity of covalent molecules
 Apply concepts associated with enthalpy changes

Explain the effect of ionic charge and radius on the

magnitude of lattice energy

 State Hess’ law of constant heat summation

 Calculate enthalpy changes from appropriate

experimental data.
WHY?
 Why do reactions happen?

 Why does methane react rapidly with oxygen to form

carbon dioxide and water vapour?

 Why does a garden fork rust if it is left outside? Why does

a rusty fork never become shiny again?

 Why does a sugar lump dissolve in a cup of tea?

Why does it never reappear out of the solution?
Introduction
 Thermochemistry is the study of the energy changes that
accompany chemical reactions.

 In the course of a chemical reaction, bonds between

atoms are broken and new bonds are made as the atoms
regroups to form new substances.

 Energy is needed to break bonds and is given out when

new bonds form

This means that the reaction is accompanied by a change

in energy mainly in the form of heat.

 So during a chemical reaction, heat flows into or out of

the reaction mixture and it returns to its original
temperature.
Definitions
 Energy- a measure of a system’s capacity to do work.
Unit= joule (J)

 Work- an energy transfer that is the result of a force

moving a body thorough a distance. Unit= joule (J)

 Heat- An energy transfer that is the result of a

temperature difference between a system and its
surroundings. Unit joule (J)

 Temperature- the property of a system that determines

the direction of heat flow between the system and its
surroundings. Heat flows from the hotter region to the
colder. Unit kelvin (K)
Definitions
 System- consists of a collection of substances involved in
the chemical reaction.

 The Surroundings- consists of everything else in the

Universe with the exception of the system.

 Internal energy (symbol U)- The energy contained within a

system. It cannot easily be measure because it is the sum
of the kinetic energies of all the particles in the system
and their potential energies.
Enthalpy
 Enthalpy (symbol H) is a term that describes the heat
content of a system. Just like internal energy, its actual
value cannot easily be measure.

 However, an enthalpy change (∆H) can easily be

measured.

 An enthalpy change is defined as the heat added to the

system under conditions of constant pressure:

enthalpy change= enthalpy of products – enthalpy of

reactants
Or using the symbols:

∆H= Hproducts - Hreactants

Enthalpy
 The typical practical procedure is to insulate the
system from its surrounding, so that no heat can
escape, and allow the temperature of the system
to change during the reaction.

 The heat needed to bring the system back to its

original temperature can then be calculated.

Heat can be evolved or it can be absorbed.

Enthalpy- Exothermic and Endothermic reactions.

 A chemical reaction that releases heat is described as an

exothermic reaction.
- It has a negative value for ∆H
- Heat flows from the system into the surroundings
- Bond making is an exothermic process

 A chemical reaction that takes in heat is described as an

endothermic reaction.
- It has a positive value for ∆H
- Heat flows from the surroundings into the system
- Bond breaking is an endothermic process.
 Enthalpy- Exothermic and Endothermic reactions.

Energy Energy

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Standard Conditions
 The value of an enthalpy change depends on the temperature,
on the physical states of the reactants (s,l, or g), the pressures
of the gaseous reactants and products and the concentrations
of solutions.

 Enthalpy changes are therefore stated under standard

conditions and are denoted by the symbol ∆Hθ

The conditions are as follows:

 298 K (25°C)
 a pressure of 1 bar (100 kPa).
 where solutions are involved, a concentration of 1 mol dm-3
Bond Energy
 The bond energy is the energy needed to break one mole of the bond to give
separated atoms, with every species being in the gas state.
 OR
 The bond energy (also called bond enthalpy) is the standard enthalpy change
associated with breaking A—B bonds into A atoms and B atoms, all species
being in the gas phase:

A—B(g)  A(g) + B(g)

For example, the H—Cl bond enthalpy is the standard enthalpy associated
with breaking H—Cl molecules into H atoms and Cl atoms.

 The values of bond enthalpies are always positive— because breaking a bond
always requires energy.

 Therefore, the enthalpy change for making a bond is equal in magnitude, but
opposite in sign.

 Side note: These bond energy values can be found in your syllabus on page 67.
Bond Energy
Bond Energy/ KJ mol-1
H—H 436
O—O 442
O—H 460
N≡N 994
O=O 496
F—F 158
Cl—Cl 244
Br—Br 193
I—I 151
H—F 562
H—Cl 431
H—Br 366
H—I 299
Make reference to your syllabus for the complete list of bonds
Calculations involving bond energies
 The following main steps can be used:

1) The first step involves calculating the standard enthalpy change

accompanying breaking the bonds in the reactant molecules.

2) The second step involves calculating the standard enthalpy change

accompanying making the bonds in the product molecules.

3) Then add together these standard enthalpy changes to obtain the overall
standard enthalpy change.

 For example, we can apply these steps to the following reaction:

2H2(g) + O2(g)  2H2O(g)

Calculations involving bond energies
2H2(g) + O2(g)  2H2O(g)
Bond Energy/
Step 1- Break into atoms 2 mol of H2 and 1 mol of O2 KJ mol-1

The total enthalpy change for breaking the molecules apart is: H—H 436
O—O 442
2 × (+436 kJ mol-1) + 1 × (+442 kJ mol-1)= +1314 kJ mol-1
The following equation can be use to illustrate what happens in the first step: O—H 460
2H2(g) + O2(g)  4H(g) + 2O(g) ∆Hθ (298 K)= +1314 kJ mol-1 Please note:
1) The values for the
Step 2- Form 2 mol of O—H bonds per mole of water produced. bond breaking process
Since there is 2 mol of water molecules produces then four O —H bonds has to be is positive while the
values for the bond
formed: 4 × ( -460 kJ mol-1)= -1840 kJ mol-1
formation is negative
The following equation can be use to illustrate what happens in the first step:
2) The bond energy
4H(g) + 2O(g)  2H2O(g) ∆Hθ (298 K)= -1840 kJ mol-1 values tend to vary
slightly depending on
which text you use.
Step 3- Sum the standard enthalpy changes to calculate the overall standard
enthalpy change: We divided by two since the
526
+1314 kJ mol + (-1840 kJ mol ) = -
-1 -1 = 263 kJ mol-1 equation produced two
moles of water we are only
2 interested in the enthalpy
change for 1 mol
Average bond energy
 The H—H bond energy is quite straight forward because the H—H bond occurs
only in the H2 molecule. On the other hand, the C—H bond is found in many
different compounds. For example, the C—H bong is found in alkanes,
aldehydes, and alcohols.

 In addition, the environment in the compound may change after the first
bond is broken. For example, the compound methane has 4 C—H bonds. When
the first C—H bond is broken, the environment in the compound changes in
such a way that the energy require to break the second (third and fourth)
bond may not be the same as the energy required to break the first bond.

 As a result, in out calculations, the bond enthalpy values used represent an

average (mean) value derived from a full range of molecules that contain a
particular bond.
 The results of calculations using average bond enthalpies will therefore show
discrepancies (inconsistencies) when compared with results from experiments
with specific molecules. It is still a useful technique though.
 This approach of using the bond enthalpy allows the enthalpy of formation
(and other reactions) to be calculated without actually conducting an
experiment.
Bond Energy
 The larger the bond energy value, the greater the energy required to break
the bond (generally). As a result, compounds that have high bond energy
values tend to be very unreactive.

 For example, N2 (or N≡N) has a bond energy value of 994 kJ mol-1 which is a
relatively high value compared to molecules like oxygen= 496 kJ mol-1.
 The strength of the nitrogen-nitrogen triple bond makes the N2 molecule very
unreactive. N2 is so inert that lithium is one of the few elements with which it
reacts at room temperature.

 In spite of the fact that the N2 molecule is unreactive, compounds containing

nitrogen exist for virtually every element in the periodic table except those in
Group VIIIA (He, Ne, Ar, and so on). This can be explained in two ways. First,
N2 becomes significantly more reactive as the temperature increases. At high
temperatures, nitrogen reacts with hydrogen to form ammonia and with
oxygen to form nitrogen oxide.

 Second, a number of catalysts found in nature overcome the inertness of N2 at

low temperature.
Bond Energy
 FACTORS ON WHICH BOND ENERGY DEPENDS:

BOND LENGTH:
Shorter the bond length, greater is the bond energy.

IONIC CHARACTER:
Greater the ionic character, greater is the bond energy.

MULTIPLE BOND:
Multiple bonds have short length, therefore, they have high bond energy.

Also, species that have delocalized electrons can a different energy value
than what is expected. For example, the bond energy value used for the C=O
bonds assumes that each C=O bond is discrete (separate). In reality, electron
density is not confined to the two C=bonds separately. It is delocalized (free
to move around) throughout the entire molecule, considerably strengthening
each bond.  O=C=O
Standard Enthalpy Changes
 1) The standard enthalpy of formation, ∆H𝑓θ , is the heat absorbed per mole
when a substance is formed from its elements in their standard states. For
example, the standard enthalpy of formation of sodium chloride is calculated
for the reaction between solid sodium chloride and gaseous chlorine
molecules, Na(s) and Cl2(g).

Based on this definition, all elements in their standard states have a value of
zero for their standard enthalpies of formation.

 2) The standard enthalpy of combustion, ∆Hθ𝑐 , is the heat absorbed per mole
when a substance is completely burned in oxygen at 1 atm. Since heat is
evolved in such a reaction, ∆Hθ𝑐 will be negative. For example,

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) ; ∆Hθ𝑐 (298K)= -890.7 kJ mol-1

Standard Enthalpy Changes
 3) The standard enthalpy of reaction, ∆Hθ𝑟 , is the heat absorbed in a
reaction at 1 atm between the number of moles of reactants shown in the
equation for the reaction.

 4) The standard enthalpy of hydration, ∆Hθhyd , is the standard enthalpy

change accompanying the production of a hydrated ion from an ion in the
gas phase. For example:
Na+(g) + water  Na+(aq) ; ∆Hθhyd (298K) = -406 kJ mol-1 s
Notice that is different from enthalpy of solution.

 5) The standard enthalpy of solution, ∆Hθsol , The heat absorbed per mole
when a substance is dissolved at 1 atm in a stated amount of solvent.
For example:
NaOH(s) + water  NaOH(aq) ; ∆Hθsol (298K) = -42.7 kJ mole-1

Two processes take place when a solid dissolves in a solvent. First, the species
in the solid become separated from each other. The standard enthalpy change
for this endothermic process is the lattice enthalpy of the solid. Secondly, the
separated species become surrounded by molecules of the solvent. This is
called solvation, or hydration (when the solvent is water).
 www.galilu.com

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Standard Enthalpy Changes
 6) The standard enthalpy of neutralisation, ∆Hθn , is the heat absorbed per
mole when an acid and a base react to form water under standard
conditions.

 7) The standard enthalpy of atomisation, ∆Hθat , is the enthalpy absorbed per

mole when a substance decomposes to form gaseous atoms.
For example:
Na(s)  Na(g) ; ∆Hθat (298K) = +108 kJ mol-1

 8) The first ionisation enthalpy, ∆Hθi.e, is the standard enthalpy change

accompanying the removal of one electron from an atom in the gas phase. For
example:
Na(g)  Na+(g) + e-(g) ; ∆Hθi.e (298K) = +498 kJ mol-1
Note that the second ionisation enthalpy, ∆Hθi.e, is similar but involves the
removal of a second electron. Na+(g)  Na2+(g) + e-(g); ∆Hθi.e (298K) = +4560 kJ mol-1
Standard Enthalpy Changes
 9) The electron affinity (electron-gain enthalpy), ∆Hθe , is the standard
enthalpy change accompanying the addition of one electron to an atom in the
gas phase.
For example:
Cl(g) + e-(g)  Cl-(g) ; ∆Hθe (298K) = -351 kJ mol-1

Notice that the process of electron gain for chlorine is an exothermic one, so
the enthalpy change has a negative sign.

 10) The lattice enthalpy, ∆Hθlat , is the standard enthalpy change

accompanying breaking of a solid lattice into separate ions In the gas phase.

For example,
NaCl(s)  Na+(g) + Cl+(g) ; ∆Hθlat (298K) = + 787 kJ mol-1

Notice that the products are not in the aqueous form. In other words, there is
a different between the lattice enthalpy, the enthalpy of hydration, and the
enthalpy of solution.
 Note that the terms
‘energy’ and ‘enthalpy’
are often times used
Lattice Energy interchangeably

 Lattice energy is a measure of the strength of the inter-ionic attraction.

The magnitude of lattice energy depends on two main factors:

1) The ionic charge: The greater the charges on the ions, the greater the The prediction is quite close to
attraction between them, and the greater will be the lattice enthalpy. the ratio of the observed values.
For example, sodium fluoride and magnesium oxide have similar NaF ∆Hθlat (298K) = +926 kj mol-1
structures. The halide is of the form M+F- and the oxide is M+O2-. The MgO ∆Hθlat (298K) = +3800 kJ mol-1
attraction between the ions is proportional to the product of the
charges. The lattice energy of the oxide is expected to be four time that
of the fluoride.
Sodium Halides

2) The radius: The smaller the distance between the ions, the greater NaF ∆Hθlat (298K) = +926 kj mol-1
the attraction between them, and the greater will be the lattice energy. For NaCl ∆Hθlat (298K) = +787 kj mol-1
example, the sizes of the halide ion increase in the order F- < Cl- < Br- < I-. NaBr ∆Hθlat (298K) = +752 kj mol-1
Lattice energies for sodium halides decrease in the same order. NaI ∆Hθlat (298K) = +705 kj mol-1

Potassium Halides
- The potassium ion is larger than the sodium ion, with the result that the
values for the potassium halides are smaller than those for the KF ∆Hθlat (298K) = +821 kj mol-1
corresponding sodium compounds KCl ∆Hθlat (298K) = +717 kj mol-1