GENG 208

Thermodynamics

The Second Law of Thermodynamics

Instructor: Dr. Mariam Itani

 Introducing & Motivating the Second Law
 It is a matter of everyday experience that there is a definite direction for
spontaneous processes.
 Object at elevated temperature Ti placed in contact with atmospheric air at T0
eventually cools to the temperature of its much larger surroundings.
 In conformity with the conservation of energy, the decrease in internal energy of
the body appears as an increase in the internal energy of the surroundings.
 The inverse process would not take place spontaneously, even though energy
could be conserved: The internal energy of the surroundings would not decrease
spontaneously while the body warms from T0 to its initial temperature.
 Introducing & Motivating the Second Law
 Air held at high pressure pi in a closed tank flows spontaneously to the lower-pressure
surroundings at p0 when the valve is opened. Eventually fluid motions cease, and all of the
air is at the same pressure as the surroundings.
 Drawing on experience, it should be clear that the inverse process would not take place
spontaneously, even though energy could be conserved: Air would not flow spontaneously
from the surroundings at p0 into the tank, returning the pressure to its initial value.
 The inverse process would not take place spontaneously, even though energy could be
conserved, and 1st law of thermodynamics is not violated: The air would not return
spontaneously to its initial pressure while its internal energy and/or that of its surroundings
decreases.
 Introducing & Motivating the Second Law
 In each case, the initial condition of the system can be restored but not in a
spontaneous process.

 Some auxiliary devices would be required. Also in each case, a fuel or electrical
input normally would be required for the auxiliary devices to function.

 Foregoing discussion indicates that not every process consistent with the principle
of energy conservation can occur. An energy balance alone neither enables the
preferred direction to be predicted nor permits the processes that can occur to be
distinguished from those that cannot.

 In simple cases as the one considered, experience can let us conclude if a process
can occur spontaneously and in what direction. However, in complex problems a
guide principle is necessary to find the direction and final equilibrium state of a
process. This principle is called the second law of thermodynamics.
 Opportunities for Developing Work
 Instead of allowing the object to cool and reach an equilibrium state with the
surroundings, we could have delivered the released energy by heat transfer to a
system undergoing a power cycle that develops a net amount of work.

 In this case we make use of the available energy instead of wasting it and losing it
to the surroundings.

 Similarly, the air at high pressure could have been entered in a turbine to produce
power instead of letting the air reach equilibrium directly with the surrounding
and waste the available energy.

 Thus, when an imbalance exists between two systems, there is an opportunity for
developing work that would be irreversibly lost if the systems were allowed to
come into equilibrium in an uncontrolled way.
 Opportunities for Developing Work
 Recognizing this possibility for work, we can pose two questions:
1. What is the theoretical maximum value for the work that could be obtained?
2. What are the factors that would prevent the realization of the maximum value?

 Of course there is a limit on the value of the work that could be obtained. Also in
real situations, even the best available devices would be subject to factors such as
friction that would prevent the attainment of the theoretical maximum work.

 The second law of thermodynamics provides the means for determining the
theoretical maximum and evaluating quantitatively the factors that prevent
attaining the maximum.
 Aspects of the Second Law
 There are many important uses of the 2nd law, including means for:
1. predicting the direction of processes.
2. establishing conditions for equilibrium.
3. determining the best theoretical performance of cycles, engines, & other devices.
4. evaluating quantitatively the factors that prevent the attainment of the best
theoretical performance level.
 Other uses of the second law include:
5. defining a temperature scale independent of the properties of any thermometric
substance.
6. developing means for evaluating properties such as u and h in terms of properties
that are more readily obtained experimentally.

 The above statements makes it hard to have one statement that represents the 2nd
law of thermodynamics, so 3 statements of the 2nd law will be introduced.
 Statements of the Second Law
 Three alternative statements of the second law of thermodynamics:
1) Clausius statement,
2) Kelvin–Planck statement, and
3) entropy statement.
 1-Clausius Statement of the Second Law
Clausius Statement of the Second Law asserts that:
It is impossible for any system to operate in such a way that the sole result would
be an energy transfer by heat from a cooler to a hotter body.
 The Clausius statement does not rule out the possibility of transferring energy by heat
from a cooler body to a hotter body, for this is exactly what refrigerators and heat
pumps accomplish.
 However, as the statement “sole result” suggests, when a heat transfer from a cooler
body to a hotter body occurs, there must be other effects within the system, its
surroundings, or both, that are accomplishing the heat transfer.
 If the system operates in a thermodynamic cycle, its initial state is restored after each
cycle, so the only place that must be examined for such other effects is its surroundings.
 2-Kelvin–Planck Statement of the Second Law
A- Introducing the concept of a thermal reservoir:
 A thermal reservoir, or simply a reservoir, is a

special kind of system that always remains at

constant temperature even though energy is
added or removed by heat transfer.
 A reservoir is an idealization, of course, but

such a system can be approximated in several

examples: Earth’s atmosphere, large bodies of
water (lakes, oceans), a large block of copper,
and a system consisting of two phases at a
specified pressure.
 2-Kelvin–Planck Statement of the Second Law
B- Note that:
The devices that convert heat to work:
1. They receive heat from a high-
temperature source (solar energy,
oil furnace, nuclear reactor, etc.).
2. They convert part of this heat to
work (usually in the form of a
rotating shaft).
3. They reject the remaining waste
heat to a low-temperature sink
(the atmosphere, rivers, etc.).
Work can always be converted to 4. They operate on a cycle.
heat directly and completely, but Heat engines and other cyclic devices
the reverse is not true. usually involve a fluid to and from
Part of the heat received which heat is transferred while
by a heat engine is undergoing a cycle. This fluid is called
converted to work, while the working fluid.
the rest is rejected to a
sink or cold body.
 2-Kelvin–Planck Statement of the Second Law
A steam power plant
B- Note that:

In the cycle:
 2-Kelvin–Planck Statement of the Second Law
C- Note that: Thermal Efficiency

 Some heat engines perform better than others (convert more of the heat
they receive to work).
 Even the most efficient heat engines reject almost one-half of the energy
they receive as waste heat.
 2-Kelvin–Planck Statement of the Second Law
D- Note that: Can we save Qout?

In a steam power plant,

the condenser is the device
where large quantities of
waste heat is rejected to
rivers, lakes, or the
atmosphere.
Can we not just take the
condenser out of the plant and
save all that waste energy?
The answer is, unfortunately, a
A heat-engine cycle cannot be completed without firm no for the simple reason
rejecting some heat to a low-temperature sink.
that without a heat rejection
Every heat engine must waste some energy by process in a condenser, the
transferring it to a low-temperature reservoir in cycle cannot be completed.
order to complete the cycle, even under
idealized conditions.
 2-Kelvin–Planck Statement of the Second Law
E- Kelvin–Planck statement of the second law:
It is impossible for any system to operate in a thermodynamic cycle and deliver a net
amount of energy by work to its surroundings while receiving energy by heat transfer
from a single thermal reservoir.
 The Kelvin–Planck statement does not rule out the

possibility of a system developing a net amount of work

from a heat transfer drawn from a single reservoir. It only
denies this possibility if the system undergoes a
thermodynamic cycle.
 No heat engine can have a thermal efficiency of 100%.

The impossibility of having a 100% efficient heat engine is

not due to friction or other dissipative effects. It is a
limitation that applies to both the idealized and the
actual heat engines.
 2-Kelvin–Planck Statement of the Second Law
F- The equivalence of the Clausius and Kelvin–Planck statements of the second law.:
Proof that the violation of the Clausius statement
leads to the violation of the Kelvin–Planck statement.
The system on the left transfers QC from cold reservoir
to hot reservoir by heat transfer without other effects
occurring and thus violates the Clausius statement.
The system on the right operates in a cycle while
receiving QH (greater than QC) from hot reservoir,
rejecting QC to cold reservoir, and delivering work Wcycle
to surroundings.
Consider the combined system which consists of the
cold reservoir and the two devices. The combined
system can be regarded as executing a cycle because
one part undergoes a cycle and the other two parts
experience no net change in their conditions. The
combined system receives energy (QH - QC) by heat
transfer from a single reservoir, hot reservoir, and
produces an equivalent amount of work. Accordingly,
the combined system violates the Kelvin–Planck
statement.
 Thus, a violation of the Clausius statement implies a
violation of the Kelvin–Planck statement.
 2-Kelvin–Planck Statement of the Second Law
G- The equivalence of the Clausius and Kelvin–Planck statements of the second law.:
Proof that the violation of the Kelvin–Planck statement
leads to the violation of the Clausius statement.
The system on the left gets QH from hot reservoir by
heat transfer and produces a work output and thus
violates the Kelvin–Planck statement.
The system on the right operates in a cycle while
QH = QH receiving work and taking heat from the cold reservoir
and transferring heat to the hot reservoir, just like a heat
pump or refrigeration cycle.
Now consider the combined system which consists of
the two devices. The combined system has no work
Qc done. Heat is transferred from the cold reservoir and
also from and back to the hot reservoir. Since we are
taking heat from the cold reservoir and delivering net
heat to the hot reservoir with no work input, the
combined system violates the Clausius statement.
 Thus, a violation of the Kelvin–Planck statement
implies a violation of the Clausius statement as well.
 3-Entropy Statement of the Second Law

 Mass and energy are familiar examples of extensive properties used in

thermodynamics.
 Entropy is another important extensive property. How entropy is evaluated and
applied is introduced later on in Chapter 6.
 Unlike mass and energy, which are conserved, entropy is produced or generated
within systems whenever non-idealities (called irreversibilities) such as friction are
present.
 The Entropy Statement of the second law:
It is impossible for any system to operate in a way that entropy is destroyed.

 To date, no experiment has been conducted that contradicts the second law in its
different statements, and this should be taken as sufficient proof of its validity.