The Second Law of Thermodynamics:

Clausius Statement
• Related to refrigerators or
heat pumps
• “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.”

An impossible Refrigerator
Kelvin–Planck vs. Clausius
Statement
• Both are negative statements, and a negative statement
cannot be proved.
• To date, no experiment has been conducted that
contradicts the statement, and this is sufficient proof of
its validity.
• Both statements are equivalent in their consequences,
and either statement can be used as the expression of
the second law of thermodynamics.
• Any device that violates the Kelvin–Planck statement
also violates the Clausius statement, and vice versa.
 A perpetual-motion machine that
violates the second law of
A perpetual-motion machine that
thermodynamics (PMM2).
violates the first law (PMM1).
Perpetual-motion machine: Any device that violates the first or the second
law.
A device that violates the first law (by creating energy) is called a PMM1.
A device that violates the second law is called a PMM2.
Despite numerous attempts, no perpetual-motion machine is known to have
worked. If something sounds too good to be true, it probably is.
• A reversible process is one carried out
infinitely slowly, so that the process can be
considered as a series of equilibrium states, and
the whole process could be done in reverse
with no change in magnitude of the work done
or heat exchanged.
• Of course this cannot be done since it would take
an infinite time.
• All real processes are irreversible: they cannot
be done infinitely slowly, there can be turbulence
in the gas, friction will be present, and so on.
• Why are we interested in reversible processes?
• (1) they are easy to analyze and
• (2) they serve as idealized models (theoretical limits) to which actual
processes can be compared.
• Some processes are more irreversible than others.
• We try to approximate reversible processes. Why?

Reversible processes deliver the most and consume

the least work.
Two familiar
reversible processes.
 • The factors that cause a process to be
irreversible are called irreversibilities.
• They include friction, unrestrained expansion,
Friction mixing of two fluids, heat transfer across a finite
renders a temperature difference, electric resistance,
process inelastic deformation of solids, and chemical
irreversible. reactions.

Irreversibilitie
s
(a) Heat
transfer
through a
temperature
difference is
irreversible, Irreversible
and (b) the compression
reverse and
process is expansion
impossible. processes.
 Internally and Externally Reversible Processes
• Internally reversible process: If no irreversibilities occur within the boundaries of
the system during the process.
• Externally reversible: If no irreversibilities occur outside the system boundaries.
• Totally reversible process: It involves no irreversibilities within the system or its
surroundings.
• A totally reversible process involves no heat transfer through a finite temperature
difference, no nonquasi-equilibrium changes, and no friction or other dissipative
effects.

A reversible process involves

no internal and external Totally and internally reversible heat
irreversibilities. transfer processes.
CARNOT ENGINE = IDEAL ENGINE
• In the early nineteenth century, the French
scientist N.L. Sadi Carnot (1796 – 1832) studied
in detail the process of transforming heat into
mechanical energy.
• Goal to increase inefficiency.
• In 1824 Carnot invented, on paper, the Carnot
engine. This is the ideal engine.
Carnot's Engine
• The Carnot engine makes use of a reversible
cycle.
• This cycle is called the Carnot cycle and the
working substance is an ideal gas.
• 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
Carnot refrigeration cycle.
• 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
Carnot refrigeration cycle.

• The Carnot heat-engine cycle and the Carnot

refrigeration cycle are two sides of the same
thermodynamic process, often referred to as the
Carnot cycle.
Carnot Cycle
 THE CARNOT
PRINCIPLES

Proof of the first Carnot principle.

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.
2. The efficiencies of all reversible heat engines operating between the
same two reservoirs are the same.
Thermodynamic Temperature
Scale
• Lord Kelvin define a
thermodynamic
temperature scale as:
• The Thermodynamic Temperature Scale is a way of measuring
temperature based on the fundamental principles of thermodynamics.
One common example of this scale is the Kelvin scale.
• Celsius vs. Kelvin:
• We're familiar with the Celsius scale where water freezes at 0 degrees and boils at 100
degrees under normal atmospheric pressure.
• The Kelvin scale is similar but starts at a different point. Zero Kelvin (0 K) is the lowest
possible temperature where nothing could be colder and no heat energy remains in a
substance.
• Absolute Zero:
• Absolute zero, which is 0 Kelvin, is the point at which particles in matter have minimal
motion. It's the lowest temperature possible and corresponds to -273.15 degrees Celsius.
• Increments:
• On the Kelvin scale, the size of each degree is the same as on the Celsius scale. So, a
change of 1 degree Celsius is equivalent to a change of 1 Kelvin.
• No Negative Kelvin:
• Unlike Celsius or Fahrenheit, Kelvin doesn't use negative values. Zero Kelvin
is absolute zero, and temperatures are always positive.
Carnot Efficiency and the Second Law
Irreversible HE : Reversible HE =
Carnot Efficiency =
Max. Efficiency

Carnot’s Theorem:
• All reversible engines operating between the same
two constant temperatures TH and TL have the
same efficiency.
• Any irreversible engine operating between the
same two temperatures will have an efficiency less
than this.
Carnot Efficiency
• Carnot efficiency is the best known reversible
engine. This is the highest efficiency a heat engine
operating between the two thermal energy
reservoirs at temperatures TL and TH can have.
• 3 situation:
Assignment 3

An engine manufacturer makes the following

claims: The heat input per second of the engine
is 9.0 kJ at 475 K. The heat output per second is
4.0 kJ at 325 K. Do you believe these claims?
Example 6-5
• A Carnot heat engine receives
500 kJ of heat per cycle from a
high-temperature source at
652°C and rejects heat to a low-
temperature sink at 30°C.
Determine (a) the thermal
efficiency of this Carnot engine,
and (b) the amount of heat
rejected to the sink per cycle.
Solution
(a) Efficiency of Carnot heat engine is:

(b) The amount of heat rejected QL:

The Quality of Energy
• Consider the Carnot heat
engine rejecting heat to a
sink at 303 K. Now let us
examine how the thermal
efficiency varies with the
source temperature (TH).
• Conclusion: the higher
the temperature, the
higher the efficiency and,
therefore, the higher the
quality of the energy.
 Lesson learned
• Work is a more valuable form of energy than heat
since 100 percent of work can be converted to
heat, but only a fraction of heat can be converted
to work.
THE CARNOT REFRIGERATOR AND
HEAT PUMP
• A refrigerator or a heat pump that operates on the reversed
Carnot cycle is called a Carnot refrigerator, or a
Carnot heat pump.
• The coefficient of performance (COP) of any
refrigerator or heat pump, reversible or irreversible:

• The COP of reversible refrigerator or heat pump:

COP of Carnot R and HP
• 3 situations:

• Same situations can be made for heat pump by

replacing COPR with COPHP.
Example
• An inventor claims to have
developed a refrigerator that
maintains the refrigerated space at
35°F while operating in a room
where the temperature is 75°F and
that has a COP of 13.5. Is this claim
reasonable?
• The performance of this refrigerator is:

• This is the highest COP a refrigerator. Since the

COP claimed by the inventor is above this
maximum value, the claim is false.
Example 6-7
• A heat pump is to be used to heat a
house during the winter. The house is
to be maintained at 21°C at all times.
The house is estimated to be losing
heat at a rate of 135,000 kJ/h when
the outside temperature drops to 5°C.
Determine the minimum power
required to drive this heat pump.
Solution
• The heat pump must supply heat to the house at a rate of
QH 135,000 kJ/h or 37.5 kW.

• The COP of a reversible heat pump is:

• The required power input to this heat pump is

Summary
• Introduction to the second law
• Thermal energy reservoirs
• Heat engines
▫ Thermal efficiency
▫ The 2nd law: Kelvin-Planck statement
• Refrigerators and heat pumps
▫ Coefficient of performance (COP)
▫ The 2nd law: Clasius statement
• Perpetual motion machines
• Reversible and irreversible processes
▫ Irreversibilities, Internally and externally reversible
processes
• The Carnot cycle
▫ The reversed Carnot cycle
• The Carnot principles
• The thermodynamic temperature scale
• The Carnot heat engine
▫ The quality of energy
• The Carnot refrigerator and heat pump
• Thank you