Spantaneous – Dispersal - E quality

System - Surrounding

Hot – Cold reservoir

What are the 1st and The 2nd Thermodynamics
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The Second Law of thermodynamics
can be expressed in terms of the entropy:

The entropy of an isolated system increases in the course of a

spontaneous change:
ΔStot > 0

where Stot is the total entropy of the system and its surroundings.

Thermodynamically, irreversible processes

(like cooling to the temperature of the surroundings and the
free expansion of gases) are spontaneous processes,
and hence must be accompanied by an increase in total entropy.
Disperse - diffuse
❑ Water is heated on a stove. Which of the following
temperature changes results in the greatest change in entropy?

1. from 10oC to 20oC

2. from 45oC to 55oC
3. from 80oC to 90oC
4. all have the same entropy change
 We explained how processes that take place spontaneously always proceed in a direction that leads to the spreading and sharing of thermal energy.
• A ball falls
• A gas expands and solutions mix because the thermal energy their molecules possess get spread over a larger volume of space.

□ Because all natural processes lead to the spreading and sharing of thermal energy, and because entropy is a measure of the extent to which energy is dispersed
in the world, it follows that:

In any spontaneous macroscopic change, the entropy of the world increases.

In other words, all spontaneous change leads to an increase in the entropy of the world.

□ At first sight, this might seem to be inconsistent with our observations of very common instances in which there is a clear decrease in
entropy, such as the freezing of a liquid, the formation of a precipitate, or adsorption.

But it’s the entropy of the system plus surroundings that counts! It is important to understand that the criterion for spontaneous change
is the entropy change of the system and the surroundings— that is, of the “world”, which we denote by ΔS total:
A quantitative example

The freezing of water

We know that liquid water will spontaneously change into ice when the temperature drops below 0°C at 1 atm pressure. Since the entropy of the solid is less
than that of the liquid, we know the entropy of the water (the system here) will decrease on freezing. The amount of decrease is found by dividing the heat of
fusion of ice by the temperature for the reversible pathway, which occurs at the normal freezing point:

Δssystem = − 6000J/mol : 273K=−21.978J/mol

If the process is actually carried at 0°C, then the heat of fusion is transferred to the surroundings at the same temperature, and the entropy of the surroundings
increases by
Δssurroundings = 6000J/mol : 273K=21.979J/mol

so that ΔStotal = 0. Under these conditions the process can proceed in either direction (freezing or melting) without affecting the entropy of the world; this means
that both ice and liquid water can be present simultaneously without any change occurring; the system is said to be in equilibrium.

Suppose now that the water is supercooled to –1°C before it freezes.

Δssurroundings = 6000J/mol : 273K = 22.059J/mol

The total entropy change is now

ΔStotal=(–21.978+22.059)J K–1mol–1 = +0.081 JK–1mol–1

indicating that the process can now occur (“is spontaneous”) only in the one direction.

Note that in order to actually freeze water, it must be cooled to very slightly below its normal freezing point. Freezing of water is of course an irreversible process
(once it starts, it cannot be stopped except by raising the temperature by a finite amount), and the positive value of ΔStotal tells us that this process will occur
spontaneously at temperatures below 273 K. Under these conditions, the process is driven by the entropy increase of the surroundings resulting from flow of the
heat of fusion of water into the surroundings.
1. For each part of the diagram first determine, which of the state functions describing the gas (p, V, T) are
constant and which are proportional to one another. Then decide how to draw the pV diagram.

2. If the volume of gas

•increases, then the gas performs work (expands),
•is constant, then neither the gas nor the surroundings perform work,
•decreases, then the work is done by the surroundings (gas is compressed), i.e. we consider the work of the gas to
be negative.

The internal energy of an ideal gas is proportional to the temperature, i.e. when the temperature changes, the
internal energy also changes the same way.
The heat supplied or released can be determined by the law of conservation of energy, which in this case is usually
called the First Law of Thermodynamics.
The VT diagram shows:
In the segment AB the volume of the gas is directly proportional to the temperature. This means that in this
phase the pressure is constant, it is an isobaric process. In the pV diagram it is represented by a horizontal line.
We can see that the volume in the first phase (from A to B) increases. Therefore, in the pV diagram state A has
to be placed on the left side and state B on the right side.
In the segment BC the volume is constant; it is an isochoric process, in pV diagram represented by the vertical
line. Since the temperature decreases between state B and state C, the pressure also decreases. Therefore,
in the pV diagram state C has to be placed under state B.
The segment CA represents an isothermal process = the temperature remains constant. In the pV diagram
shown by a part of a hyperbole.