Chapter 23-Entropy & Gibbs Energy

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ENTROPY AND GIBBS

FREE ENERGY
CHAPTER 23:
The Laws of Thermodynamics, Entropy, and Gibbs Free
Energy

 https://
www.youtube.com/watch?v=8N1BxHgsoOw
What is entropy? - Jeff Phillips

 https://www.youtube.com/watch?v=YM-uykVfq_E
Introducing entropy

 Entropy is a measure of the  The system of magnesium reacting


dispersal of energy at a specific with sulfuric acid in a test tube to
temperature. Entropy can also be form magnesium sulfate and
thought of as a measure of the hydrogen releases energy to the
randomness or disorder of a surroundings. The surroundings
system. The higher the randomness include:
or disorder, the greater the  ■■ the solvent (in this case water)
entropy of the system.
 ■■ the air around the test tube
 A system is the part under
investigation. In chemistry this is  ■■ the test tube itself
the chemical reaction itself, i.e.  ■■ anything dipping into the test
reactants being converted to tube (e.g. a thermometer).
products.
Introducing entropy

 Changes that tend to continue to  Entropy can also be thought of as a


happen naturally are called dispersal of energy, either from
spontaneous changes. the system to the surroundings or
 When a light is applied, methane gas from the surroundings to the
reacts with oxygen in a spontaneous system. The system becomes
reaction to form carbon dioxide and energetically more stable when it
water. The reaction is spontaneous becomes more disordered.
because the methane continues to burn
in the oxygen until either the methane
or oxygen is completely used up. For a
reaction to be spontaneous, it does not
need to happen rapidly. Many
spontaneous reactions are slow or need
an input of energy to start them.
Chance and spontaneous change

 Diffusion If you spill a few drops of


perfume in a closed room with no air
draughts, the smell spreads gradually
throughout the room. The molecules
in the perfume vapour, which are
responsible for the smell, move
randomly in straight lines until they
collide with air molecules, other
perfume molecules or with the walls
of the room. After collision, the
perfume molecules change direction.
This process of random movement and
random collisions of molecules is
called diffusion.
Diffusion and number of ways
Comparing entropy values

 To make any comparison of  ■■ a pressure of 105Pa


entropy values fair, we must  ■■ a temperature of 298K (25
use standard conditions. These °C)
standard conditions are the
same as those used for ΔH:  ■■ each substance involved in
the reaction is in its normal
physical state (solid, liquid or
gas) at 105Pa and 298K.
From the values in the table and other
data we can make some generalisations:
 Gases generally have much higher entropy values than liquids, and liquids
have higher entropy values than solids. There are exceptions to this. For
example, calcium carbonate (solid) has a higher entropy value than
mercury (liquid).

 Simpler substances with fewer atoms have lower entropy values than more
complex substances with a greater number of atoms. For example, for
calcium oxide, CaO, S —O(standard entropy) = 39.7 JK–1mol–1 but for
calcium carbonate, CaCO3, S —O(standard entropy) = 92.9 JK–1mol–1.
Carbon monoxide, CO, has a lower entropy value than carbon dioxide,
CO2.
From the values in the table and other
data we can make some generalisations:
 For similar types of substances, harder substances have a lower entropy value. For example,
diamond has a lower entropy value than graphite and calcium has a lower entropy value than lead.

 For a given substance the entropy increases as a solid melts and then changes to a vapour (see
Figure 23.5). For example, the molar entropy of ice just below its melting point is 48.0 JK–1mol–1;
the molar entropy for water is 69.9 JK–1mol–1, but just above its boiling point, the value increases
to 188.7 JK–1mol–1.
 There is a gradual increase in entropy as the temperature of a substance is increased. Increasing
the temperature of a solid makes the molecules, atoms or ions vibrate more. Increasing the
temperature of a liquid or gas increases the entropy because it increases the disorder of the
particles.
 When a substance melts or vaporises, there is a large increase in entropy because there is a very
large increase in the disorder of the particles.
When a solid changes to a liquid:

■ the regularly arranged lattice of particles close


together in the solid changes to

 ■■an irregular arrangement of particles, which


are close together but rotate and slide over each
other in the liquid.
When a liquid changes to a vapour:

 ■■ the irregular arrangement of


particles in the liquid which are
close together and rotating changes
to

 ■■ an irregular arrangement of
particles, which are free to move
around rapidly because they are far
apart from each other.
Entropy changes in reactions
 In a chemical reaction, if we compare the entropies of the reactants and
products, we can try to explain the magnitude of the entropy change and
whether or not it increases or decreases.
 We will assume that gases have high entropy and solids have low entropy. If
there is a change in the number of gaseous molecules in a reaction, there is
likely to be a significant entropy change. This is because high values of
entropy are associated with gases. The more gas molecules, there are, the
greater is the number of ways of arranging them and the higher the entropy.
For example in the reaction:
Calculating entropy changes

Entropy changes in exothermic and endothermic reactions

 ■ For an exothermic reaction, the energy released to the surroundings


increases the number of ways of arranging the energy. This is because the
energy goes into rotation and translation (movement from place to place) of
molecules in the surroundings. So there is likely to be an increase in entropy
and an increased probability of the chemical change occurring spontaneously.

 ■■ For an endothermic reaction, the energy absorbed from the surroundings


decreases the number of ways of arranging the energy. So there is likely to be
a decrease in entropy and a decreased probability of the chemical change
occurring spontaneously.
Total entropy change

 If the total entropy change


increases, the entropy change is
positive, e.g. ΔS —O total is +40
JK–1mol–1 . The reaction will then
occur spontaneously. We say that
the reaction is feasible.
 If the total entropy change
decreases, the entropy change is
negative, e.g. ΔS —O total is –40
JK–1mol–1. The reaction is then not
likely to occur.
Calculating the entropy change of the system
Calculating the entropy change of the system
Calculating the entropy change of the
surroundings
Calculating the entropy change of the
surroundings
Calculating total entropy change
Entropy in equilibrium reactions

 As mixing proceeds, the rate of


increasing disorder decreases as
more and more NO2 molecules
are formed from N2O4. At some
stage in the reaction, the rate of
the forward reaction equals the
rate of the backward reaction.
Equilibrium has been reached.
Entropy and temperature

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