WEEK 1
Second law of thermodynamics
Consider a bar of metal that is hot at one end and cold at the other. .Heat will be conducted
spontaneously along the bar from the hot to the cold end and until temperature is uniform. The
reversal could be attained if heat is allowed to pass from one end to a machine where it is
converted into an equivalent amount of work. By means of friction the work is reconverted into
an equivalent amount of heat that is now transferred to the other end of the bar
But it is a matter of experience that a complete reversal is impossible due to the fact that, “heat
cannot be completely converted into an equivalent amount of work without causing other
changes in some part of the system or its surroundings.’’
This is the 2nd law of thermodynamics “all natural or spontaneous process (i.e. those occurring
without external aid) are thermodynamics irreversible in character.
Reasons for studying the second law
It predicts the direction in the time of processes
.It aids in determination of equilibrium constants
.It allows one to determine peak performance of practical devices
.It enables one to frame analysis of the factors which inhibit the realization of peak
performances
.It also allows a rational definition of the absolute temperature scale
Definitions
I. Isolated system
Thermodynamics system enclosed by immovable walls through which neither matter nor
energy can pass
II. Closed system
Enclosed by selective walls through which energy can pass as heat or work but not matter
III. Open system
Both matter and energy can enter or exit through the boundaries.
Other statements of the 2nd law of thermodynamics include
1. Entropy based statement.
The entropy of an isolated system can never decrease with time
2. Clausius statement
Heat cannot, by itself, pass from a colder to a hotter body. Air conditioner move heat
from cold regions to hot regions, but work input is required in form of electricity.
3. Kelvin- Planck statement
It is impossible for any system to operate in a thermodynamic cycle and deliver a net
amount of work to its surroundings while receiving an energy transfer of heat from a
single thermal reservoir.
4. Kelvin statement
No process is possible whose so results is complete conversion of heat to work in other
words no engine is capable of converting all the heat QH to work without any Qc formed.
In general there is no ideal engine and efficiency is less than one (ղ< 1)
5. Clausins statement
No process is possible whose so results is transfer of heat from cold to hot. For example
using the idea of a refrigerator you want to extract more Qc for less work i.e in the
process of zero work you would still be able to transfer heat (it’s not possible) because
(no ideal refrigerator )
Second law of thermodynamics
The second law of thermodynamics states that for any spontaneous process then overall change
in entropy (∆S) must be greater than or equal to zero. Yet spontaneous chemical reactions can
result in a negative change in entropy. This does not contradict the second law, however, since
such a reaction must have a sufficiently large negative change in enthalpy (heat energy). The
increase in temperature of the surroundings increase energy because of the exothermicity of the
reaction so that it overcompensates for the negative ∆S of the system since,
the overall,
∆S universe = ∆S surrounding + ∆S system,
The overall change in entropy is still positive.
There laws were developed in the 18 th during the industrial revolution when engines were being
developed where coal was being used to run the engines.
One should think of making the best from the machine i.e efficiency
Efficiency is defined as
work
efficiency =
heat produced from the coal
W
η =
QH
W is less than QH due to heat loss
We can say that
W Q H −Q C
η= = ≤1
QH QH
Refrigerator
Refrigerator work in reverse. In order to cool the food stuffs energy from the electricity is used in
the machine which extracts heat from the food stuff
Performance (efficiency) of a refrigerator has no constraints and it can be less or more than one.
QC (heat from food )
η=
W (Given energy or electricity )
Q
η= C
QH −QC
Spontaneous processes
There are processes which take place either on their own or by certain initiation. These are
irreversible processes that occur without any energy input to the system.
For an isolated system the change is internal energy is given by
∆ U= q +w =0 +0= 0
For example
I. Expansion of gas into a vacuum (gas and vacuum)
When the partition is removed the gas expands and fills the vacuum
∆ U= q +w =0 +0= 0
II. Gas mixing (Neon and Helium)
In both cases there is increase in disorder that is there is increase in entropy (∆S)
For natural spontaneous processes the ∆S > 0
For ideal process ∆S = 0
Entropy is the measure of randomness or disorder. Spontaneity depends on a combination of
enthalpy ∆H and entropy ∆S. For a reaction to be spontaneous the Gibbs free energy (∆G ) must
be negative. Gibbs free energy is given by the following relationship.
∆G = ∆H – T ∆S
Where
∆H is the change in enthalpy
T is the absolute temperature
∆S is the change in entropy
For any spontaneous reaction there is always increase in entropy of the universe (∆S universe is
always positive).
∆S universe = ∆S system + ∆S surrounding
If ∆S system it can still be spontaneous as long as the ∆S surrounding is larger and positive
Example H2O (l) → H2O (g)
Summary
The second law of thermodynamics states that for any spontaneous process then overall change
in entropy (∆S) must be greater than or equal to zero.
∆S universe = ∆S surrounding + ∆S system
For a reaction to be spontaneous the Gibbs free energy (∆G) must be negative. Spontaneous
processes take place either on their own or by certain initiation. For an isolated system there is no
change in internal energy.
Assignment
Kelvin and clausius statements are the most close in defining the 2 nd law of thermodynamics.
Show that the two statements are the same.