The Second Law of Thermodynamics (I)

(This slides summarize the content of Nov.

24, 2003)

•1 Introduction to the Second Law

• 2 Temperature Reservoirs
• 3 Heat Engines
Introduction to the Second Law
Common Processes for Explaining the Second Law
(1) A cup of (2) Transferring (3) Transferring
hot coffee heat to a wire heat to a paddle
does not get will not wheel will not
hotter in a generate cause it to
cooler room. electricity. rotate.
Introduction to the Second Law (continued)
• The first law of thermodynamics places no restriction
on the direction of a process, but satisfy the first law
does not ensure that that that process will actually
occur. This inadequacy of the first law to identify
whether a process can take place is remedied by
introducing the second law of thermodynamics.
• The second law also asserts that energy has quality as
well as quantity. More of high-temperature energy can be
converted to work, and thus it has a higher quality than
the same amount of energy at a lower temperature.
• The second law also can be used in determining the
theoretical limits of heat engines and refrigerators, as
well as predicting the degree of completion of chemical
reactions.
Thermal Energy Reservoirs
• In the development of the second law of
thermodynamics, it is very convenient to have a
hypothetical body with a relatively large thermal energy
capacity that can supply or absorb finite amounts of
heat without undergoing any change in temperature,
such as body is called thermal energy (heat) reservoir
or temperature reservoir.
• Examples are atmosphere, two-phase systems, and
even the air in a room.
• A reservoir that supplies energy in the form of heat is
called a source, and one that absorbs energy in the
form of heat is called a sink.
Heat Engines
Devices (figure at right) that converts
heat into work is called heat engines,
which can be characterized by the
following:
1. They receive heat from high-
temperature source.
2. They convert part of this heat to work.
3. They reject the remaining waste heat
to a low-temperature sink.
4. They operate on a cycle.
Heat engines and other cyclic devices usually involve a
fluid to and from which heat is transferred while
undergoing a cycle. This fluid is called the working fluid.
Thermal Efficiency
The fraction of the heat input that
is converted to net work output
is a measure of the performance
of a heat engine and is called the
thermal efficiency ηth.
Desired output
performance =
Required input
Net work output Wnet ,out Qout
η th = = = 1−
Total heat input Qin Qin

The thermal efficiencies of work-producing devices are

relatively low. 25% for ordinary spark-iginition
automobile engines; 40% for diesel engines; and 60% for
large combined gas-steam power plants.
Can we save Qout?
Every heat engine must waste some energy by
transferring it to a low-temperature reservoir in order to
complete the cycle, even under idealized conditions. It
requires at least two reservoirs for continuous
operation.
A heat- engine
cycle cannot
be completed
without
rejecting some
heat to a low
temperature
sink.
The Second Law of Thermodynamics:
Kelvin-Plank Statement
It is impossible for any device that operates on a cycle
to receive heat from a single reservoir and produce a
net amount of work.

It implies that: No heat engine can have a thermal

efficiency of 100%.

Note that the impossibility of having a 100% efficient

heat engine is a limitation that applies to both idealized
and the actual heat engines.
The second Law of Thermodynamics: Clausius Statement

There are two classical statements

of the second law − the Kelvin-
Plank statement, which is related
to heat engines, and the Clausius
statement, which is related to
refrigerators or heat pumps. The
Clausius statement is expressed
as follows:
It is impossible to construct a
device that operates in a cycle and
produces no effect other than the
transfer of heat from a lower-
temperature body to a higher-
temperature body.
Equivalence of the Two Statements
Proof that the violation of the Kelvin-Planck statement
leads to the violation of the Clausius Statement.
Perpetual-Motion Machines
A device that violates the first law of thermodynamics (by
creating energy) is called a perpetual-motion machine of
the first kind (PMM1). No energy input to but output from
the system.
A device that violates the second law of thermodynamics
is called a perpetual-motion machine of the second kind
(PMM2).
Reversible and Irreversible Processes
A reversible process is defined as a process that can be
reversed without leaving any trace on the surroundings.
Reversible processes can be viewed as theoretical limits
for the corresponding irreversible ones. The more closely
we approximate a reversible process, the more work
delivered by a work-producing device or the less work
required by a work-consuming device.
The concept of reversible processes leads to the
definition of the second-law efficiency for actual
processes, which is the degree of approximation to the
corresponding reversible process.
Irreversibilities
The factors that cause a process to be irreversible are
called irreversibilities. They include:
•friction
•unstrained expansion
•mixing of two gases
•heat transfer across a finite temperature difference
• flow of electric current through an electric resistance
• inelastic deformation of solids
• chemical reactions.
 Totally Reversible

A process is called totally reversible, or simply reversible,

if it involves no irreversibilities within the system
(internally reversible) or its surroundings (externally
reversible). A totally reversible process involves no heat
transfer through a finite temperature difference, no non-
quasi-equilibrium changes, and no friction or other
dissipative effects.
The Carnot Cycle
The best known reversible cycle is the
Carnot cycle, first proposed in 1824 by
French engineer Sadi Carnot. The four
reversible processes that make up the
Carnot cycle are as follows:
Reversible Isothermal Expansion:
Temperature remains at TH, the
amount of total heat transferred to the
gas during this isothermal process is
QH.
Reversible Adiabatic Expansion:
Temperature drops from TH to TL, the
process is reversible as well as
adiabatic.
The Carnot Cycle (continued)
Reversible Isothermal Compression:
Temperature remains at TL, a
reversible heat transfer process, the
amount of total heat transferred to
the gas during this isothermal
process is QL.
Reversible Adiabatic Compression:
Temperature rises from TL to TH, the
process is reversible as well as
adiabatic compression process,
which completes the cycle.
P-υ Diagram of Carnot Cycle

The P-υ diagram of Carnot

cycle is shown in the figure at
right.

Area under curve 1-2-3 corresponds to the work done by

the gas, area under curve 3-4-1 corresponds to the
work done on the gas.
The Reversed Carnot Cycle
The Carnot heat-engine cycle
is a totally reversible cycle.
Therefore, all the processes
that comprise it can be
reversed, in which case it
becomes the refrigeration
cycle.
The P-υ diagram of the reversed Carnot cycle is the same
as the one given for Carnot cycle, except that the
direction of the processes are reversed, as shown in
figure at right. Heat in the amount of QL is absorbed from
the low-temperature reservoir, heat in the amount of QH
is rejected to a high-temperature reservoir, and a work
input of Wnet,in is required to accomplish all this.
The Carnot Principles
1. The efficiency of an irreversible
heat engine is always less than the
efficiency of a reversible one
operating between the same two
reservoirs.
The Carnot Principles
(continued)

2. The efficiencies of all

reversible heat engines
operating between the same two
reservoirs are the same.