Chapter Three

The second law of thermodynamics

At the end of this chapter you will learn:

-the second law of thermodynamics and its applications
- Apply the second law to some familiar processes
- the concept of entropy
∙ Relate changes in entropy to T and P for substances in the ideal-gas state

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 Why we need it?
A process must satisfy the first law in order to occur. However, satisfying the first law alone does not
ensure that the process will take place.
The first law can not express a lot of processes like

Transferring heat to a wire A cup of hot coffee does

will not generate electricity. not get hotter in a cooler
room.

Second law is useful:

• provide means for predicting the direction of processes,
• establishing conditions for equilibrium,
• determining the best theoretical performance of cycles, engines and other devices.

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 Second Law Statement
• 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.
• All efforts to devise a process for the continuous conversion of heat completely into work
or into mechanical or electrical energy have failed.
• 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.

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3
 Second Law
Statements
Spontaneous changes are those which, if carried out under the proper
conditions, can be made to do work. If carried out reversibly they yield
a maximum amount of work. In irreversible (spontaneous) processes
the maximum work is never achieved.

No apparatus can operate in such a No process is possible which

way that its only effect (in system and consists solely in the transfer of heat
surroundings) is to convert heat from one temperature level to a higher
absorbed by a system completely into one. .
work done by the system.

Kelvin-Planck statement Clausius statement,

• No heat engine can have a thermal • No heat pump that operates
efficiency 100 percent. continuously
• As for a power plant to operate, the • Heat pump will transfer heat from a
working fluid must exchange heat with lower temperature body to a higher
the environment as well as the
Nov-21 temperature body. 4
furnace.
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6
 Heat Engines
Heat engines, devices or machines that produce work from heat in a cyclic process.

Heat engine differ considerably from one another,

but all can be characterized :

o they receive heat from a high-temperature

source
o they convert part of this heat to work
o they reject the remaining waste heat to a low
Temperature sink atmosphere
o they operate on a cycle

The actual meaning of hat engine is a

thermodynamic systems which operating in cycle
Receive a heat and deliver a net of work.

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 Heat Engines
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: The
word cyclic requires that the system be restored periodically to its original state.

Liquid water at ambient temperature is

pumped into a boiler at high pressure.
Heat from a fuel (heat of combustion of
a fossil fuel or heat from a nuclear reaction)
is transferred in the boiler to the water,
converting it to high-temperature steam
at the boiler pressure.
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.
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.

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• Heat engine cycles are absorption of heat into the system (QH= Qin) at a
high temperature (TH), rejection of heat to the surroundings (QC = Qout) at
a lower temperature (TL) , and production of work (W).
• 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.
• What about in real application????????????
• There is a magnitude of the energy wasted in cycle.
• A measure of the performance that is called the thermal efficiency. It
can be expressed in terms of the desired output and the required input

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• For a heat engine the desired result is the net work done and the input is the heat
supplied to make the cycle operate (the working fluid of heat engine absorb heat I
QHI from a hot reservoir , produces a net amount of work IWI, discard heat I QcI to
cold reservoir, and return to its initial state.
• The thermal efficiency is always less than 1 or less than 100 percent.

• Applying the first law to the cyclic heat engine

The cycle thermal efficiency may be written as

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 Heat Pump
• is a thermodynamic system which operating in a cycle removes heat
from the low temperature body to high temperature body by the
application of external energy in the form of work on the pump.
• Refrigerator operates exactly like heat pump except that the desired
output is the amount of heat removed out of the system
• The index of performance of a heat pumps or refrigerators are
expressed in terms of the coefficient of performance. (COP)
𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡 𝑄𝐻 𝑄𝐻 𝑇𝐻
• 𝐶𝑂𝑃 = =𝑊 =𝑄 =𝑇
𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛 𝑛𝑒𝑡,𝑖𝑛 𝐻 −𝑄𝐿 𝐻 −𝑇𝐿

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• The thermal efficiencies of actual and reversible heat engines
operating between the same temperature limits compare as follows

• The coefficients of performance of actual and reversible refrigerators

operating between the same temperature limits compare as follows

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 The Carnot Cycle (Carnot engine)
• The characteristics of such an ideal engine were described by N. L. S. Carnot in 1824.
He devised a classical ideal cycle named after him that formed the basis for the
mathematical first statement of second law of thermodynamics
• It operate between two heat reservoir in such a way that all heat absorbed at constant
temperate of the hot reservoir and all heat rejected at constant temperature of the cold
reservoir.
• The thermal efficiency of a heat engine depends on the degree of reversibility of its
operation. Indeed, a heat engine operating in a completely reversible manner is very
special, and is called a Carnot engine.
• The thermal efficiency is 100%, Ideal, Theoretical, Reversible, Maximum work,
maximum temperature

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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 | QH| 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.
Step 4: 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 rejection of heat | QC| to the cold reservoir.

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Two adiabatic reversible processes and two isothermal processes
The Carnot Cycle for Ideal Gas:
• The cycle traversed by an ideal gas serving as the working fluid in a
Carnot engine is shown by a PV diagram. It consists of four reversible
steps:
• a → b Adiabatic compression with temperature rising from TC to TH.
• ∙ b → c Isothermal expansion to arbitrary point c with absorption of heat
QH.
• ∙ c → d Adiabatic expansion with temperature decreasing to TC.
• ∙ d → a Isothermal compression to the initial state with rejection of heat
QC. 𝑇 𝐶
η= 1−
𝑇𝐻

• (Derive it)

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• Example 1
• From a reservoir at 600 K, 1000 J of heat is transferred to an engine that
operates on the Carnot cycle. The engine rejects heat to a reservoir at 300 K.
Determine the thermal efficiency of the cycle and the work done by the engine
Example 2
• A central power plant rated at 800000kW, generated from steam at 585K and
discards heat to a river at 285K. If the thermal efficiency of the plant is 70% of
the maximum possible value, how much heat is discarded to the rive at rated
power.
• Example 3
• One kilogram of water is heated in a heat pump from a temperature of 294K to
boiling point of 373K and completely vaporized. The latent heat o vaporization is
1960 kJ/kg. Determine:
a- the minimum amount of work
b- the heat transferred to work at temperature 294K.

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 Entropy:
• Entropy by Carious ( in a turning ) insidious of transformation
• Entropy ( microscopic – macroscopic)
• Entropy is a measure of number of ways that energy can be distributed in a system of molecules

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 Entropy:
• A thermodynamic quantity representing the unavailability or degradation of
energy. often interpreted as the degree of disorder or randomness in the
system.
• The entropy of a system is affected only by the nature of the matter under
consideration and the state in which it exists. And it is not affect by the
external position of the body or its motion relative to other bodies.
• - The entropy of the system is increased by the addition of heat through any
mechanism or from source.
• - The increase in entropy accompanying the addition of a given amount of
heat to a system with lowering the temperature at which the heat is added.
And its lead to a great degradation of energy than at a higher temperature.
• - In addition , in order to complete the definition of entropy, the nature of the
process should also be specified. The change in entropy (a state function)
is dependent only on the initial and final states and not on the path.
• - The amount of heat transferred to measure the increase in entropy through
the term (Q / T ) is the degradation of higher forms of energy into heat, which
is possible only in a reversible process. Therefore be measured as (QR/ T ) ,
where QRis the heat transferred when the process is occurring reversible.

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• The following specifications are important to define the entropy:
1- the amount of heat transferred.
2- The temperature level at which the transfer occurs
3- The nature of the process, whether reversible or irreversible.
• So::
𝑑𝑄𝑅
• 𝑑𝑆 =
𝑇
• The entropy change of any system is undergoing reversible
process so integration gives
𝑑𝑄𝑅
• ∆𝑆 = ‫׬‬
𝑇
• If the process is reversible and adiabatic then dS=0 and the
system called (isentropic)

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• Entropy Changes of an Ideal Gas:
• From first law of thermodynamic
• dU = dQ –dW
• For reversible process dU = dQR – p.dV
• By substitution of enthalpiy, then
• dQR = dH – V.dP
• For ideal gas dH = cpig.dT and V = RT/P
𝑇2 𝑖𝑔 𝑑𝑇 𝑃2
• ∆𝑆 = ‫ 𝑝𝑐 𝑇׬‬. 𝑇 − 𝑅. 𝑙𝑛
1 𝑃1
𝑇
𝑖𝑔 ‫ 𝑇׬‬2 𝑐𝑝𝑖𝑔 .𝑑𝑇/𝑇
1
• 𝑐𝑝𝑚𝑠 = 𝑇
𝐿𝑛(𝑇2 )
1

• Hence
𝑖𝑔 𝑇2 𝑃2
• ∆𝑆 = 𝑐𝑝𝑚𝑠 𝐿𝑛 − 𝑅. 𝑙𝑛
𝑇1 𝑃1
• Entropy Changes of Liquid:
• Consider unit mass of a liquid which will ultimately be raised to unit
mass of vapor at constant pressure.
• For the unit mass of liquid,
• dQ = cpL. - dT
• where: cpL is specific heat capacity of the liquid at constant pressure.
• Dividing eq. throughout by T,then
• dQ/T = cpL. dT/T
• Since dS=dQ/T for this case dS= cpL. dT/T
• Integrating this equation from initial state to final state:
• [S2–S1] = cpL.ln (T2/T1)

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 MATHEMATICAL STATEMENT OF
SECOND LAW
For isolated system the net entropy is:

ΔS (surrounding)+ ΔS ( system ) ≥ 0
The validity of the above equations can be verified for a process in which an
amount of heat Q is transferred from a heat source at temperature T1 to a heat
sink at T2. The change in entropy of the heat source is –Q/T1 and that of the
heat sink is Q/T2. The entropy change of the heat source and sink add up to
give the following result
𝑄 𝑄 𝑇1−𝑇2
ΔSt = - 𝑇 + 𝑇 =Q 𝑇 𝑇
1 2 1 2

The mathematical statement of the second law is that every process

proceeds in such a direction the total entropy changes ΔSt associated
with it is always positive, the process is possible.ΔSt ≥ o
ΔSt > o (positive) then process is possible
ΔSt = o then process is reversible
ΔSt < o (negative then process is impossible

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 LOST WORK
• Work that is wasted as the result of irreversibility in a process is called lost work, Wlost,
and is defined as the difference between the actual work of a change of state and the ideal
work for the same change of state. Thus by definition,
• W lost ≡ W s − W ideal
• The efficiency of real heat engine is
ɧ= T1 – T2 / T1
• The work of any engine can be calculate according to its efficiency
•
𝑇1 − 𝑇2
𝑊=𝑄
𝑇1
The work which lost by the irreversibility of the process is
𝑇1 − 𝑇2
𝑊 = 𝑄𝑇2
𝑇1
𝑊𝐿𝑜𝑠𝑡 = 𝑇2 (∆𝑆)𝑡𝑜𝑡𝑎𝑙

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• Example 4
• (0.3)kg of air at 350 kN/m2 and 350C reverse heat at constant volume
until its pressure becomes 700 kN/m2 . Determine the change of
entropy during each process. Take cp = 1.006 kJ/kG.K and cv = 0.717
kJ/kg.K
• Example 5
• Oil at 500 K is to be cooled at a rate of 5000 kg/h in a counter-
current exchanger using cold water available at 295 K. A temperature
approach of 10 K is to be main-tained at both ends of the exchanger.
The specific heats of oil and water are respectively 3.2 and 4.2 kJ/kg
K. Determine the total entropy change in the process.
• Example 6
• One kilogram of superheated steam at 1.5 MPa and 523 K (H = 2923.5
kJ/kg, S = 6.71 kJ/kg K) is contained in a piston-cylinder assembly.
The unit is kept at ambient conditions of 300 K and the steam
condenses to saturated liquid (H = 845 kJ/kg, S = 2.32 kJ/kg K) at
constant pressure. Calculate the change in entropy and check whether
the process is reversible or not.
• See Example ( example 5.3 and 5.4),INTRODUCTION TO CHEMICAL
ENGINEERING THERMODYNAMICS,Sixth Edition,Smith.
• See Example ( example 4.20) in textbook,A Textbook ofChemical Engineering
Thermodynamics,SECOND EDITION,K.V. NARA YANAN.