This is easily explained with

the help of a property,

called entropy.
 Chapter 5
The Second Law of Thermodynamics
• Introduce the concept of entropy, an essential thermodynamic
property
• Present the second law of thermodynamics, which reflects the
observation that limits exist to what can be accomplished even by
reversible processes
• Apply the second law to some familiar processes
• Relate changes in entropy to changes in T, P and V for substances
in the ideal-gas state
• Present entropy balances for open systems
• Demonstrate the calculation of ideal work and lost work for flow
processes
5.1 AXIOMATIC STATEMENTS OF THE SECOND LAW

The Second Law of Thermodynamics states that the state of entropy of the
entire universe, as an isolated system, will always increase over time. The
second law also states that the changes in the entropy in the universe can
never be negative.
THERMAL ENERGY RESERVOIRS

A hypothetical body with a relatively large thermal

energy capacity (mass × specific heat) that can supply or
absorb finite amounts of heat without undergoing any
change in temperature.

Such a body is called a thermal energy reservoir, or

just a reservoir. e.g. ocean.

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 (Fig. 6–7).
Thermal energy reservoirs are often referred to as
heat reservoirs since they supply or absorb energy
in the form of heat.
Application of the Second Law to Simple Heat Transfer:

from Eq. (5.1). Because T is constant, integration gives

Let the temperatures of the reservoirs be TH and TC with TH > TC.
Heat quantity Q, transferred from one reservoir to the other, with QH = −QC
and the entropy changes of the reservoirs at TH and at TC are:

Because the heat-transfer process is irreversible, Eq. (5.2) requires a positive

value for ΔStotal, and therefore
QC(TH −TC) > 0
So, QC must be positive, which means that heat flows into the reservoir at TC, i.e., from
the higher to the lower temperature.
No process is possible which consists solely of the transfer of heat from one temperature
level to a higher one.
Application of the Second Law to Heat Engines:
work can be converted to heat directly and completely, but converting heat to work requires
the use of some special devices. These devices are called heat engines.
Heat engines differ considerably from one another, but all can be characterized by the
following (Fig. 6–9):
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.).
4. They operate on a cycle.
Application of the Second Law to Heat Engines
The second law imposes restrictions on how much of their heat
intake can be converted into work

Page 175

If the engine is totally If the process is reversible in

ineffective, W = 0 all respects, then ΔStotal = 0

Carnot engine.
 The second law does not prohibit the continuous production of work from heat, but it
does place a limit on how much of the heat taken into a cyclic process can be
converted into work.
The thermal efficiency of a heat engine is defined as the ratio of the work
produced to the heat supplied to the engine.

Or, Qin= QH
Now,
From the general expression of work done, W = QH − QC

And work done by the Carnot engine,

We can write,

Carnot engine
 and, Qin= QH

EXAMPLE 6–1 Net Power Production of a Heat Engine

Heat is transferred to a heat engine from a furnace at a rate of 80 MW. If the rate of waste heat
rejection to a nearby river is 50 MW, determine the net power output and the thermal efficiency
for this heat engine.
6–15 A steam power plant receives heat from a furnace at a rate of 280
GJ/h. Heat losses to the surrounding air from the steam as it passes
through the pipes and other components are estimated to be about 8
GJ/h. If the waste heat is transferred to the cooling water at a rate of 145
GJ/h, determine (a) net power output and (b) the thermal efficiency of
this power plant.
Application of the Second Law to Heat Pumps:
the Carnot cycle can traverse in the opposite direction, and becomes a heat pump

FIGURE 6–20
The objective of a
refrigerator is to
remove QL from the
cooled space.
Carnot heat pump or refrigerator.

Here, work is required, and it is used to “pump” heat from the lower-temperature heat
reservoir to the higher-temperature heat reservoir.

Refrigerators are heat pumps with the “cold box” as the lower-temperature reservoir
and some portion of the environment as the higher-temperature reservoir.
Coefficient of Performance

The usual measure of quality of a heat pump

is the coefficient of performance (COP),
defined as the heat extracted at the lower
temperature divided by the work
required, both of which are positive
quantities with respect to the heat pump:

For a Carnot heat pump this coefficient is

FIGURE 6–19
the value of COP can be greater than unity. Basic components of a refrigeration
system and typical operating
conditions.
A food department is kept at -12C by a refrigerator in an
environment at 30C. The total heat gain to the food department
is estimated to be 3300 kJ/h and the heat rejection in the
condenser is 4800 kJ/h. Determine the power input to the
compressor, in kW and the COP of the refrigerator.
The Second Law of Thermodynamics: Kelvin–Planck 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.
related to heat engines

The Second Law of Thermodynamics: Clausius Statement

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.
related to refrigerators or heat pumps
ENTROPY
Paths ACB and ADB represent two arbitrary reversible processes for which

𝑑𝑄𝑟𝑒𝑣 𝑑𝑄𝑟𝑒𝑣
∆𝑆 𝑡 = න 𝑎𝑛𝑑 ∆𝑆 𝑡 = න
𝐴𝐶𝐵 𝑇 𝐴𝐷𝐵 𝑇

Because ∆𝑆 𝑡 is a property change, it is independent of

path and is given by 𝑆𝐵𝑡 − 𝑆𝐴𝑡 .
If the fluid is changed from state A to state B by an
irreversible process, the entropy change is again
Figure 5.3: Two reversible paths ∆𝑆 𝑡 = 𝑆𝐵𝑡 − 𝑆𝐴𝑡
joining equilibrium states A and B.

The entropy change of a heat reservoir, is given by Q/T, where Q is the quantity of heat
transferred to or from the reservoir at temperature T, whether the transfer is reversible or
irreversible.
If a process is reversible and adiabatic, dQrev = 0; and d𝑆 𝑡 = 0.
When a system undergoes an irreversible process between two equilibrium states, the
entropy change of the system resulting only from the transfer of heat is evaluated by
application of Eq. (5.1) to an arbitrarily chosen reversible process that accomplishes the
same change of state as the actual process.
Eq. (5.1)
 ENTROPY CHANGES FOR THE IDEAL-GAS STATE
For one mole or a unit mass of fluid undergoing a mechanically reversible process
in a closed system, the first law, Eq. (2.7), becomes:

Problem 7–75,7-77 of Cengel

With these substitutions and division by T,

Integration from an initial state at conditions T0

and P0 to a final state at conditions T and P gives:

Also, prove that

See page 352 of Cengel for details
 Example 5.2

Solution 5.2

Exponentiation of both sides of this equation leads to the given equation.

Is entropy considered energy?
No, entropy is the measure of a system's thermal energy per unit temperature
that is unavailable for doing useful work.

Because work is obtained from ordered molecular motion, the amount of

entropy is also a measure of the molecular disorder, or randomness, of a
system.

Why is entropy not energy?

Entropy is very different from
energy. Entropy is not conserved
but increases in all real processes.
Reversible processes (such as in
Carnot engines) are the processes in
which the most heat transfer to work
takes place and are also the ones that
keep entropy constant.
 Example 5.4
A 40 kg steel casting (𝐶𝑃 = 0.5 kJ⋅kg-1 K-1 ) at a temperature of 450°C is quenched in 150 kg of
oil (𝐶𝑃 = 2.5 kJ⋅ kg-1 K-1) at 25°C. If there are no heat losses, what is the change in entropy of
(a) the casting, (b) the oil, and (c) both considered together?

Solution 5.4
The final temperature t of the oil and the steel casting is found by an energy balance.
Because the change in energy of the oil and steel together must be zero,
(40)(0.5)(t− 450) + (150)(2.5)(t − 25) = 0
Solution yields t = 46.52°C.

(a) Change in entropy of the casting: (b) Change in entropy of the oil:

= 26.13 kJ⋅ K-1

Note that although the total entropy change is positive, the entropy of the casting has decreased.
ENTROPY BALANCE FOR OPEN SYSTEMS Entropy is not conserved!!

For a steady-state flow process With only one entrance and one exit

The limiting case for which SG= 0 applies, is when

• The process is internally reversible within the control volume
• Heat transfer between the control volume and its surroundings is reversible
5.7 CALCULATION OF IDEAL WORK
In any steady-state flow process which is completely reversible,
the entropy generation is zero,
for a uniform surroundings temperature Tσ

Substituting this expression for Q ∙ in the energy balance

Ws (rev) is given the name ideal work, Wideal ,

kinetic- and potential-energy terms are negligible compared with the others

For the special case of a single stream flowing through the control volume
The thermodynamic efficiency can be expressed as

𝑊ሶ 𝑠 (or 𝑊𝑠) is the actual work of a process

5.8 LOST WORK

𝑊𝑙𝑜𝑠𝑡 ≡ 𝑊𝑠 − 𝑊𝑖𝑑𝑒𝑎𝑙

For the case of a single surroundings temperature 𝑇𝜎

𝑊ሶ 𝑙𝑜𝑠𝑡 = 𝑇𝜎 𝑆𝐺ሶ
Heat in the amount of 150 kJ is transferred directly from a hot reservoir at TH =
550 K to two cooler reservoirs at T1 = 350 K and T2 = 250 K. The surroundings
temperature is Tσ = 300 K. If the heat transferred to the reservoir at T1 is half
that transferred to the reservoir at T2, calculate:
(a) The entropy generation in kJ·K-1.
(b) The lost work.
How could the process be made reversible?

Problem 5.44: Do yourself