ENERGETICS

Enthalpy and
Entropy
 Entropy
• Entropy (S) : Can be thought of as a
measure of the disorder of a system

 In general, greater disorder means

greater entropy. It can be thought as a
force in the universe that pushes
everything toward disorder and chaos.
 Trends in Entropy
• Entropy for gas phase is greater than that of
liquid or solid of same substance
– I2 (g) has greater entropy than I2 (s)
• More complex structures have greater
entropy
– C2H6 (g) has greater entropy than CH4 (g)
• Allotropes - more ordered forms have lower
entropy
– Diamond has lower entropy than graphite
Entropy Changes in a System
Qualitative
• S solid < S liquid

Copyright McGraw-Hill 2009

Entropy Changes in a System
Qualitative
• Sliquid < Svapor

Copyright McGraw-Hill 2009

Entropy Changes in a System
Qualitative
• Spure < Saqueous

Copyright McGraw-Hill 2009

Entropy Changes in a System
Qualitative
Slower temp < Shigher temp

Copyright McGraw-Hill 2009

 Enthalpy
 We already know about enthalpy.
Enthalpy is related to the amount of
energy that is lost or gained by a system
during a normal chemical process.
 We have seen both endothermic and
exothermic processes in lab.
Enthalpy (∆H)
 Total kinetic and potential energy of a system under constant
pressure.
 The internal energy of a reactant or product cannot be
measured, but their change in enthalpy (heat of reaction) can.

 A change in enthalpy occurs during phase changes, chemical

reactions and nuclear reactions.
If heat is absorbed during the reaction, ΔH is
positive;
if heat is released, then ΔH is negative.
Chemical Energetics -Bond energies
Chemical Reactions- Old bonds between
atoms are broken
 Bond breaking - endothermic
• Energy is always required to be given to break
a bond. Bond breaking is always endothermic.
Chemical Reactions- New bonds between
atoms formed
 Bond making - exothermic
• Energy is always released when a bond is
formed. Bond making is always exothermic.
 Bond energies
The energy released when a bond is formed or
absorbed when it is broken is called the bond
energy.

e.g. the C-H bond in methane has a bond energy

of 413 KJ/mol
Examples of bond energies

Bond Bond energy KJ/mol

H-H 436
Cl-Cl 242
H-Cl 431
C-H 413
C-C 347
C-O 335
O=O 498
Where does the energy come
from?

In any chemical reaction, the SAME NUMBER of

bonds are broken as are made.

So how do exothermic reactions

give out energy to the
surroundings?
 Bond Energy
If the SAME NUMBER of bonds are made and broken,
how can energy be given out in an exothermic reaction?

The answer is that different chemical

bonds have different amounts of energy
in them.by a strong bond.
Carbon is joined to a hydrogen
412 kJ of energy is needed to break this bond,
and to separate the atoms
The same amount of energy is given out when the bond
is formed.

H O has a bond energy of 463 kJ

C==O has a bond energy of 743 kJ
 Energy Level
Diagrams
These are drawn as
graphs.
They are used to show exothermic and
endothermic reactions.
The x axis shows time, the y axis shows
energy.

Energy

Time
 Exothermic Reactions
An exothermic energy diagram looks like
this.

reactants

}
Energy
Energy
released
products

Time
 Exothermic reaction
The energy need to break the bonds is less than the energy
released when new bonds are made

C + 4H + 4O
energy

Energy needed to
Energy released by
break bonds
CH4(g) + 2O2(g) forming bonds

Energy released
CO2(g) + 2H2O(l)

“reaction path”
 Exothermic Reactions
Combustion and respiration are exothermic
reactions. e.g. burning methane (natural gas).
CH4 + 2O2  2H2O + CO2

CH4 + 2O2

}
Energy

Energy
2H2O + CO2 released

Time
 Endothermic reaction
The energy need to break the bonds is more than the energy
released when new bonds are made
energy

Energy released by
Energy needed to forming bonds
break bonds
NH4NO3(l)

Energy absorbed
NH4NO3(s) + H2O (l)

“reaction path”
ΔH – Energy change in a complete reaction

If heat is given out, the reaction has lost

energy so ΔH is negative
ΔH – Energy change in a complete reaction

If heat is absorbed (reaction gets colder), the

reaction has gained energy so ΔH is positive
 Calculating ΔH
CH4(g) + 2O2(g) 2H2O(l) + CO2(g)

ΔH value negative --> energy released --> exothermic

reaction

ΔH value positive --> energy absorbed --> endothermic

reaction

∆H= ∆H(bonds broken in reactants) − ∆H(bonds made in

products)
 Calculating ΔH

CH4(g) + 2O2(g) 2H2O(l) + CO2(g)

Bonds broken = 4 x (C-H) + 2 x (O=O)

= 4 x 413 + 2 x 498
= 1662 + 996 = 2658 KJ/mol
 Calculating ΔH
CH4(g) + 2O2(g) 2H2O(l) + CO2(g)

Bonds broken = 4 x (C-H) + 2 x (O=O)

= 4 x 413 + 2 x 498
= 1662 + 996 = 2658 KJ/mol
Bonds made = 4 x (O-H) + 2 x (C=O)
= 4 x 464 + 2 x 805
= -1856 + -1610 = 3466 KJ/mol
 Calculating ΔH
CH4(g) + 2O2(g) 2H2O(l) + CO2(g)

Bonds broken = 4 x (C-H) + 2 x (O=O)

= 4 x 413 + 2 x 498
= 1662 + 996 = 2658 KJ/mol
Bonds made = 4 x (O-H) + 2 x (C=O)
= 4 x 464 + 2 x 805
= -1856 + 1610 = 3466 KJ/mol

∆H= ∆H(bonds broken in reactants) − ∆H(bonds made in products)

Overall Energy change = 2658 -3466 = -808 KJ/mol

(Exothermic)
Calculating Bond Energies
CH4 + 2H2O + CO2
2O
C-H bond 2 = 412
H-O bond = 463
4 of these =
4 of these = 1852
C=O bond = 743
1648 2 of these =
1486
O=O bond = 496
Total energy =
2 of these = 992 3338 kJ
released
Total energy
More energy
2640 kJ
is released by bond making than is
required
required for bond breaking, so 698 kJ of energy
is given out to the surroundings in this reaction,
so this is an exothermic reaction.
 Activation Energy
Most exothermic reactions need a bit of energy
to get them started, like lighting methane with
a match.
This energy is known as ACTIVATION ENERGY. This
energy breaks the bonds and allows atoms to
separate.
This changes the shape of the energy diagram to
this.

reactants } Activation energy

Energy

products

Time
 Why is activation energy
needed ? Separate
atoms (with
most energy):
CH4 + 2O2 1 C, 4 H, and
4O
Energy

2H2O + CO2

Time
Energy is needed to break bonds so atoms can become
separate. The separate atoms can then react
and rejoin into different compounds. If the new compounds
require less energy to form, the reaction is exothermic.
 Endothermic Reactions
Examples are photosynthesis and most electrolysis reactions.

The energy level diagrams look like this.

products

}
Energy
Energy needed
to make the
reaction work.
reactants

Time
Endothermic Reactions
In these reactions, the energy required for
bond breaking IS GREATER than the
energy released by bond making.

This means that to make endothermic

reactions take place, extra energy is
needed from an external source.
 What Will Happen?
• If more energy is needed to break bonds?

• If more energy is formed during bond making?

 What Will Happen?
• If more energy is needed to break bonds, more
heat energy will be taken in and temperature
will decrease during the reactions.
• Heat taken in – Endothermic Reactions.
• If more energy is formed during bond making,
heat will be given out and temperature will
increase.
• Heat given out – Exothermic Reactions.
 Examples in Daily Life
Exothermic Endothermic
Burning of fossil fuels melting ice cubes
making ice cubes
conversion of frost to water vapour
formation of snow in clouds
evaporation of water
condensation of rain from water vapour

cooking an egg
a candle flame
producing sugar by photosynthesis

Fire, combustion, steam condensing to Sweating,

liquid water, rusting, Lighting a match, a
hand warmer, Turning on a light. any
chemical reaction that gives off heat.
 Questions

(a) What energy source is needed for these reactions to

occur:
(i) Photosynthesis? (ii) electrolysis?
(b) Which type of reaction are these examples of?
(c) What can you say about the number of bonds broken
and made during a chemical reaction?
(d) Sketch energy level diagrams to show exothermic and
endothermic reactions.
(e) What is an exothermic reaction?
(f) Why are some reactions exothermic?
(g) What is Activation Energy, and why is it needed?
(h) Add this to the correct energy diagram sketch.