UNIT-3

The second law of Thermodynamics

• Thermodynamics is concerned with transformations of energy, and the laws of
thermodynamics describe the bounds within which these transformations are
observed to occur.
• The first law reflects the observation that energy is conserved, but it imposes no
restriction on the process direction.
• Experience indicates the existence of such a restriction, the concise statement of
which constitutes the second law.
• The differences between the two forms of energy, heat and work, provide some
insight into the second law
• Work is readily transformed into other forms of energy: for example, into
potential energy by elevation of a weight, into kinetic energy by
acceleration of a mass, into electrical energy by operation of a generator.
• These processes can be made to approach a conversion efficiency of
100% by elimination of friction, a dissipative process that transforms work
into heat.
• Indeed, work is readily transformed completely into heat, as
demonstrated by Joule's experiments.
• On the other hand, all efforts to devise a process for the continuous
conversion of heat completely into work or into mechanical or electrical
energy have failed.
• Regardless of improvements to the devices employed, conversion
efficiencies do not exceed about 40%.
• Drawing further on our experience, we know that the flow of heat
between two bodies always takes place from the hotter to the cooler
body, and never in the reverse direction.
• This fact is of such significance that its restatement serves as an
acceptable expression of the second law.
 STATEMENTS OF THE SECOND LAW OF THERMODYNAMICS

• The observations just described suggest a general restriction on processes

beyond that imposed by the first law. The second law is equally well expressed
in two statements that describe this restriction:
• Statement 1:
• No apparatus can operate in such a way that its only effect (in system and
surroundings) is to convert heat absorbed by a system completely into work
done by the system.
Statement 2:
• No process is possible which consists solely in the transfer of heat from one
temperature level to a higher one.
• Statement 1a:
• It is impossible by a cyclic process to convert the heat absorbed by a system
completely into work done by the system.
 HEAT ENGINES
• Heat engines, devices or machines that produce work from heat in a cyclic process.
• An example is a steam power plant in which the working fluid (steam) periodically returns to its
original state. In such a power plant the cycle (in its simplest form) consists of the following steps:

(1)Liquid water at ambient temperature is pumped into a boiler at high

pressure.
(2)Heat from a fuel is transferred in the boiler to the water, converting it to
high-temperature steam at the boiler pressure.
(3)Energy is transferred as shaft work from the steam to the surroundings by a
device such as a turbine, in which the steam expands to reduced pressure
and temperature
(4)Exhaust steam from the turbine is condensed by transfer of heat to the
surroundings, producing liquid water for return to the boiler, thus completing
the cycle.
• Essential to all heat-engine cycles are absorption of heat into the
system at a high temperature, rejection of heat to the surroundings at
a lower temperature, and production of work.
• In the theoretical treatment of heat engines, the two temperature
levels which characterize their operation are maintained by heat
reservoirs, bodies imagined capable of absorbing or rejecting an
infinite quantity of heat without temperature change.
• In operation, the working fluid of a heat engine absorbs heat QH from
a hot reservoir, produces a net amount of work IWI, discards heat IQcI
to a cold reservoir, and returns to its initial state.
• The first law therefore reduces to:
•  Absolute-value signs are used to make the equations independent of
the sign conventions for Q and W .
• For to be unity (100% thermal efficiency), IQcI must be zero.
• No engine has ever been built for which this is true; some heat is
always rejected to the cold reservoir. This result of engineering
experience is the basis for statements 1 and 1a of the second law.
• A heat engine operating in a completely reversible manner is very
special, and is called a Carnot engine.
• The characteristics of such an ideal engine were first described by N.
L. S. Carnot in 1824.
• The four steps that make up a Carnot cycle are performed in the
following order:
Step 1: A system at the temperature of a cold reservoir Tc undergoes a reversible
adiabatic process that causes its temperature to rise to that of a hot reservoir at TH.
Step 2: The system maintains contact with the hot reservoir at TH and undergoes a
reversible isothermal process during which heat IQHI is absorbed from the hot
reservoir.
Step 3: The system undergoes a reversible adiabatic process in the opposite
direction of step 1 that brings its temperature back to that of the cold reservoir at Tc
Step4:The system maintains contact with the reservoir at Tc, and undergoes a
reversible isothermal process in the opposite direction of step 2 that returns it to its
initial state with IQcI to the cold reservoir.
• A Carnot engine operates between two heat reservoirs in such a way
that all heat absorbed is absorbed at the constant temperature of the
hot reservoir and all heat rejected is rejected at the constant
temperature of the cold reservoir.
• Any reversible engine operating between two heat reservoirs is a
Carnot engine; an engine operating on a different cycle must
necessarily transfer heat across finite temperature differences and
therefore cannot be reversible.
 Carnot's Theorem

• Statement 2 of the second law is the basis for Carnot's theorem:

For two given heat reservoirs no engine can have a thermal
efficiency higher than that of a Carnot engine.
• To prove Carnot's theorem assume the existence of an engine E with a
thermal efficiency greater than that of a Carnot engine which absorbs
heat IQHI from the hot reservoir, produces work IWI and discards IQHI
– IWI to a cold reservoir
• Assume an engine E with a greater thermal efficiency than a Carnot
engine for the same heat reservoirs, absorbing heat IQ’HI, producing
work IWI and discarding heat IQ’HI – IWI
If engine E has the greater efficiency,

Let the engine E drive the Carnot engine backward as a Carnot refrigerator. For this
engine/refrigerator combination, the net heat extracted from the cold reservoir is
• A central power plant, rated 800,000 kW generates steam at 585 K
and discards heat to a river at 295 K. If the thermal efficiency of the
plant is 70% of the maximum possible value, how much heat is
discarded to the river at rated power?
THERMODYNAMIC TEMPERATURE SCALES

•  In this Carnot engine to establish a thermodynamic temperature scale

that is truly independent of any material properties
• Let represent temperature on some empirical scale that identifies
temperature levels.
• Consider two Carnot engines, one operating between a hot reservoir
at temperature H and a cold reservoir at temperature and 2nd
operating between the reservoir at and a still colder reservoir at
• The heat rejected by the 1st engine IQCI is absorbed by the 2nd ;
therefore; the 2 heat heat engines working together constitute a 3rd
Carnot engine absorbing heat IQHI from the reservoir at H and
rejecting heat IQFI to the reservoir at
Ideal-Gas Temperature Scale; Carnot's Equations
•  The cycle traversed by an ideal gas serving as the working fluid in a
Carnot engine is shown by a PV diagram in Fig. It consists of four
reversible steps:
a b: Adiabatic compression until the temperature rises from Tc to TH
b c : Isothermal expansion to point c with absorption of heat IQHI
c d : Adiabatic expansion until the temperature decreases to Tc
d a : Isothermal compression to the initial state with rejection of
heat IQcI
For the isothermal steps b c and d a ,
5.2.  A Carnot engine receives 250 kW of heat from a heat-source
reservoir at 798.15 K (525°C) and rejects heat to a heat-sink reservoir at
323.15 K (50°C). What are the power developed and the heat rejected?
•5.3.
   The following heat engines produce power of 95000kW.
Determine in each case the rates at which heat is absorbed from the
hot reservoir and discarded to the cold reservoir.
(a) A Carnot engine operates between heat reservoirs at 750K and
300K.
(b) A practical engine operates between the same heat reservoirs but
with a thermal efficiency
ENTROPY
• Equation for a Carnot engine may be written: IQHI/TH = IQcI/Tc
• If the heat quantities refer to the engine (rather than to the heat
reservoirs), the numerical value of QH is positive and that of Qc is
negative.
• The equivalent equation written without absolute-value signs is
therefore QH/TH = - Qc/Tc
QH/TH + Qc/Tc = 0 --- (1)

• Thus, for a complete cycle of a Carnot engine, the two quantities Q/T
associated with the absorption and rejection of heat by the working
fluid of the engine sum to zero.
• The working fluid of a cyclic engine periodically returns to its initial
state, and its properties, e.g., temperature, pressure, and internal
energy, return to their initial values.
• Indeed, a primary characteristic of a property is that the sum of its
changes is zero for any complete cycle.
• Thus for a Carnot cycle Eq. (1) suggests the existence of a property
whose changes are given by the quantities Q /T .
• Our purpose now is to show that Eq. (1), applicable to the reversible
Carnot cycle, also applies to other reversible cycles
• The closed curve on the P V diagram of Fig. represents an arbitrary
reversible cycle traversed by an arbitrary fluid.
• Divide the enclosed area by a series of reversible adiabatic curves; since
such curves cannot intersect, they may be drawn arbitrarily close to one
another.
• Several such curves are shown on the figure as long dashed lines.
• Connect adjacent adiabatic curves by two short reversible isotherms which
approximate the curve of the arbitrary cycle as closely as possible.
• The approximation clearly improves as the adiabatic curves are more
closely spaced.
• When the separation becomes arbitrarily small, the original cycle is faithfully
represented. Each pair of adjacent adiabatic curves and their isothermal
connecting curves represent a Carnot cycle for which Eq. (1) applies.
• Each
  Carnot cycle has its own pair of isotherms TH and Tc and associated
heat quantities QH and Qc .
• These are indicated on Fig. for a representative cycle.
• When the adiabatic curves are so closely spaced that the isothermal
steps are infinitesimal, the heat quantities become dQH and dQc , and Eq.
(1) for each Carnot cycle is written:
dQH/TH + dQc/Tc = 0
• In this equation TH and Tc ,absolute temperatures of the working fluid of
the Carnot engines, are also the temperatures traversed by the working
fluid of the arbitrary cycle.
• Summation of all quantities dQ /T for the Carnot engines leads to the
integral: = 0 ----- (2)
•  where the circle in the integral sign signifies integration over the
arbitrary cycle, and the subscript "rev" indicates that the cycle is
reversible.
• Thus the quantities sum to zero for the arbitrary cycle, exhibiting the
characteristic of a property.
• We therefore infer the existence of a property whose differential
changes for the arbitrary cycle are given by these quantities.
• The property is called entropy , and its differential changes are:
dSt ----- (3)
Where St is the total (rather than molar) entropy of the system.
Alternatively, T dSt . ----- (4)
•  If a process is reversible and adiabatic, dQrev = 0; then by Eq.(3),
dSt = 0
Thus the entropy of a system is constant during a reversible adiabatic
process, and the process is said to be isentropic.
The discussion of entropy can be summarized as follows:
• There exists a property called entropy S, which is an intrinsic
property of a system, functionally related to the measurable coor-
dinates which characterize the system. For a reversible process,
changes in this property are given by Eq. (3).
• The change in entropy of any system undergoing a finite reversible
process is: St ----- (5)
• When a system undergoes an irreversible process between two
equilibrium states, the entropy change of the system is evaluated by
application of Eq. (5) to an arbitrarily chosen reversible process that
accomplishes the same change of state as the actual process.
• Integration is not carried out for the irreversible path. Since entropy
is a state function, the entropy changes of the irreversible and
reversible processes are identical.
ENTROPY CHANGES OF AN IDEAL GAS

• For one mole or a unit mass of fluid undergoing a mechanically

reversible process in a closed system, the first law, becomes:
where S is the molar entropy of an ideal gas. Integration from an initial state
at conditions To and Po to a final state at conditions T and P gives:

It is a general equation for the calculation of entropy changes of an ideal gas.

This form of the equation for entropy changes of an ideal gas may be useful when
iterative calculations are required.