The Second Law of

Thermodynamics
 INTRODUCTION

❑ Have you ever observed this process, a broken cup spontaneously

reassembling and rising up onto a table?
– This process could conserve energy and other laws of mechanics.

The first law of thermodynamics tells us that energy is

conserved. However, the absence of the process
illustrated above indicates that conservation of energy is
not the whole story. If it were, movies run backwards
would look perfectly normal to us!
 INTRODUCTION

Work can always be converted to heat directly

and completely, but the reverse is not true
INTRODUCTION
Transferring
heat to a paddle
wheel will not
cause it to
rotate.
These processes
cannot occur
even though they
Transferring are not in
heat to a violation of the
wire will not first law.
generate
electricity.
Hot pans cool
Ice cubes
down when
melt in a
taken out
warm room.
from the
stove.

Processes occur in a certain

direction, and not in the
reverse direction.
The second law of thermodynamics enables us
to determine the feasibility of a process and
hence the direction in which it will proceed.

A process must satisfy both

the first and second laws of
thermodynamics to proceed.
 MAJOR USES OF THE SECOND LAW
❑ The second law also asserts that energy has quality
as well as quantity (e.g.: A high-temperature energy
source has a higher quality since it is easier to
extract energy from it to deliver useable work). The
first law is concerned with the quantity of energy
and the transformations of energy from one form to
another with no regard to its quality.
❑ The second law of thermodynamics is also used in
determining the theoretical limits for the
performance of commonly used engineering systems,
such as heat engines and refrigerators (e.g.: A
Carnot engine is theoretically the most efficient
heat engine; its performance can be used as a
standard for other practical engines)
 THERMAL ENERGY RESERVOIRS

A source
supplies
energy in
the form of
heat, and a
sink absorbs
Bodies with relatively large it.
thermal masses can be modeled
as thermal energy reservoirs.

❑ A hypothetical body with a relatively large thermal

energy capacity (mass x specific heat) that can supply
or absorb finite amounts of heat without undergoing
any change in temperature is called a thermal energy
reservoir, or just a reservoir.
HEAT ENGINES
The devices that convert heat
to work.
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.
A steam power plant
A portion of the work output
of a heat engine is consumed
internally to maintain
continuous operation.

𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑊𝑜𝑢𝑡 − 𝑊𝑖𝑛

𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡
Thermal Efficiency
The efficiency of the heat engine is the
ratio of the work done to the heat input:
𝑊𝑛𝑒𝑡,𝑜𝑢𝑡
𝜂𝑡ℎ =
𝑄𝑖𝑛

_ 𝑊𝑛𝑒𝑡,𝑜𝑢𝑡 = 𝑄𝐻 − 𝑄𝐿

𝑄𝐻 − 𝑄𝐿
𝜂𝑡ℎ =
𝑄𝐻

𝑄𝐿
𝜂𝑡ℎ =1−
𝑄𝐻
[Example] A steam power plant produces 50 MW of net
work while burning fuel to produce 150 MW of heat
energy at the high temperature. Determine the cycle
thermal efficiency and the heat rejected by the cycle to
the surroundings.
[Example] An automobile engine has an efficiency of 20% and
produces an average of 23,000 J of mechanical work per
second during operation.
(a) How much heat input is required, and
(b) How much heat is discharged as waste heat from this
engine, per second?
A steam power plant Can we save Qout?
❑ In a steam power plant,
the condenser is the
device where large
quantities of waste heat is
rejected to rivers, lakes,
or the atmosphere.
❑ Can we not just take the
condenser out of the plant
and save all that waste
energy?
❑ The answer is,
unfortunately, a firm NO
for the simple reason that
without a heat rejection
process in a condenser,
the cycle cannot be
completed.
 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.
 Thermal Efficiency - Comparison

Even the most efficient heat

Some heat engines perform
engines reject almost one-
better than others (convert more
half of the energy they
of the heat they receive to work).
receive as waste heat.
 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.
❑ No heat engine can have a thermal
efficiency of 100 percent, or as for a
power plant to operate, the working
fluid must exchange heat with the
environment as well as the furnace.
❑ The impossibility of having a 100%
efficient heat engine is NOT due to A heat engine that violates
friction or other dissipative effects. the Kelvin–Planck statement
It is a limitation that applies to both of the second law.
the idealized and the actual heat
engines.
 Refrigerators
❑ The transfer of heat
from a low-
temperature medium
to a high-temperature
one requires special
devices called
refrigerators.
❑ Refrigerators, like
heat engines, are
cyclic devices.
❑ The working fluid used
in the refrigeration
Basic components of a refrigeration cycle is called a
system and typical operating conditions.
refrigerant.
 Coefficient of Performance
The efficiency of a refrigerator is
expressed in terms of the coefficient of
performance (COP).

𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑜𝑢𝑡𝑝𝑢𝑡 𝑄𝐿
𝐶𝑂𝑃𝑅 = =
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑖𝑛𝑝𝑢𝑡 𝑊𝑛𝑒𝑡,𝑖𝑛

_ 𝑊𝑛𝑒𝑡,𝑖𝑛 = 𝑄𝐻 − 𝑄𝐿

𝑄𝐿
𝐶𝑂𝑃𝑅 =
𝑄𝐻 − 𝑄𝐿

The objective of a refrigerator

is to remove QL from the cooled
space.
[Example] The food compartment of a refrigerator is
maintained at 4°C by removing heat from it at a rate of 360
kJ/min. If the required power input to the refrigerator
is 2 kW, determine
(i) the coefficient of performance of the refrigerator and
(ii) the rate of heat rejection to the room that houses the
refrigerator?
The Second Law of Thermodynamics:
Clasius 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.

❑ It states that a refrigerator cannot operate

unless its compressor is driven by an external
power source, such as an electric motor.
o This way, the net effect on the
surroundings involves the consumption of
some energy in the form of work, in
addition to the transfer of heat from a A refrigerator that
colder body to a warmer one. violates the Clausius
❑ To date, no experiment has been conducted statement of the
that contradicts the second law, and this should second law.
be taken as sufficient proof of its validity.
 Equivalence of the Two Statements

The Kelvin–Planck and the Clausius 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.
 Reversible and Irreversible Processes
Reversible process: A process that can be reversed without leaving any
trace on the surroundings.
Irreversible process: A process that is not reversible by itself.
❑ All the processes occurring in nature are
irreversible.
❑ 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.

Two familiar Reversible processes deliver the most and consume

reversible processes. the least work.
 The Carnot Cycle

Execution of the Carnot cycle in a closed system.

Reversible Isothermal Expansion (process 1-2, TH = constant)
Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TL)
Reversible Isothermal Compression (process 3-4, TL = constant)
Reversible Adiabatic Compression (process 4-1, temperature rises from TL to TH)
 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 Carnot refrigeration cycle.

P-V diagram of the Carnot cycle. P-V diagram of the reversed

Carnot cycle.
 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.,  th   th , Carnot
2. The efficiencies of all reversible heat engines operating between
the same two reservoirs are the same.
The Thermodynamic Temperature Scale

Lord Kelvin in 1848 used

energy as a
thermodynamic property
to define temperature
and devised a
temperature scale that
is independent of the
thermodynamic
substance.

Lord Kelvin's Carnot heat engine arrangement

 The thermal efficiency of any heat engine
QL
 th = 1 −
QH
For the Carnot engine
 th = g (TL , TH ) = 1 − f (TL , TH )
❑ Considering engines A, B, and C
Q1 Q1 Q2
=
Q3 Q2 Q3
This looks like
f (T1 , T3 ) = f (T1 , T2 ) f (T2 , T3 )

One way to define the f function is

 (T2 )  (T3 )  (T3 )
f (T1 , T3 ) = =
 (T1 )  (T2 )  (T1 )
The simplest form of  is the absolute temperature itself.
T
f (T1 , T3 ) = 3 This is the maximum possible
T1
efficiency of a heat engine
The Carnot thermal efficiency becomes operating between TH and TL.
𝑇𝐿 The temperatures are
η𝑡ℎ,𝑟𝑒𝑣 = 1 − absolute temperatures.
𝑇𝐻
 𝑄𝐻 𝑇𝐻
=
𝑄𝐿 𝑟𝑒𝑣
𝑇𝐿

Can we use C unit for

temperature here?

This temperature scale

is called the Kelvin
scale, and the
temperatures on this
scale are called absolute
temperatures.

A conceptual experimental setup to

determine thermodynamic
temperatures on the Kelvin scale by
measuring heat transfers QH and QL.
[Example] A Carnot heat engine receives 500 kJ of heat per cycle
from a high-temperature heat reservoir at 652°C and rejects heat
to a low-temperature heat reservoir at 30°C. Determine
(i) The thermal efficiency of this Carnot engine and
(ii) The amount of heat rejected to the low-temperature heat
reservoir
The Quality of Energy
As a system approaches absolute zero,
heat becomes harder to extract

𝑇𝐿
η𝑡ℎ,𝑟𝑒𝑣 = 1 −
𝑇𝐻

The fraction of heat

that can be converted to The higher the temperature
work as a function of of the thermal energy, the
source temperature. higher its quality.
The second law of thermodynamics can be
understood through considering these
processes:
❑A rock will fall if you lift it up and then let go
❑ Hot pans cool down when taken out from the
stove.
❑ Ice cubes melt in a warm room.
What’s happening in every one of those?
Energy of some kind is changing from being
localized (concentrated) somehow to becoming
more spread out.
i.e., The potential energy localized in the
rock is now totally spread out and dispersed
in:
◦ A little air movement.
◦ Little heating of air and ground.
The second law of thermodynamics states that
energy (and matter) tends to become more
evenly spread out across the universe.

Hostel room – Hostel room –

First yr. Second yr.
 What is entropy?
Entropy just measures the spontaneous
dispersal of energy: or how much energy is
spread out in a process as a function of
temperature.
 Entropy
❑ Entropy a measure of disorder in the physical system.
❑ the movement towards a disordered state is a
spontaneous process.

So in a simple equation:
"𝐸𝑛𝑒𝑟𝑔𝑦 𝑑𝑖𝑠𝑝𝑒𝑟𝑠𝑒𝑑"
𝐸𝑛𝑡𝑟𝑜𝑝𝑦 =
𝑇
Entropy couldn't be expressed without the inclusion of
absolute temperature.

▪ Entropy change ΔS shows us exactly how important to

a system is a dispersion of a given amount of energy
 Entropy
For a reversible engine has the relation between the
heat transferred and the reservoir temperatures:
𝑄𝐿 𝑇𝐿 𝑄𝐿 𝑄𝐻
= _ =
𝑄𝐻 𝑇𝐻 𝑇𝐿 𝑇𝐻

❑ This quantity, Q/T, is the same for both reservoirs.

This conserved quantity is defined as the change in
entropy (ΔS).
𝑄
∆𝑆 = (if the temperature is constant)
𝑇

Otherwise,
𝑑𝑄
∆𝑆 = න
𝑇
 Entropy
Unlike energy, entropy is NOT conserved

Proof:
A real engine will operate at a lower efficiency than a
reversible engine; this means that less heat is converted
to work.
𝑄𝐿 𝑇𝐿 𝑄𝐿 𝑇𝐿 𝑄𝐿 𝑄𝐻
𝜂𝑖𝑟𝑟𝑒𝑣 < 𝜂𝑟𝑒𝑣 _ 1 − <1− _
𝑇𝐻 _ 𝑄𝐻 𝑇𝐻
> >
𝑄𝐻 𝑇𝐿 𝑇𝐻

𝑄𝐿 𝑄𝐻
∆𝑆𝑡𝑜𝑡𝑎𝑙 = − >0
𝑇𝐿 𝑇𝐻
Any irreversible process results in an increase of entropy.
[Example] An irreversible engine operating between the
temperatures of 550 K and 300 K extracts 1200 J of
heat from the hot reservoir and produces 450 J of work.
How much entropy is created in the process?
 Entropy

For a Carnot engine: 𝑄𝐿 𝑄𝐻

=
𝑇𝐿 𝑇𝐻
• Heat supplied QH is positive
• Heat rejected QL is negative

−𝑄𝐿 𝑄𝐻
_ =
𝑇𝐿 𝑇𝐻

𝑄𝐿 𝑄𝐻
_ + =0
𝑇𝐿 𝑇𝐻
 Entropy in Cyclic Process
Any cyclic process can be written as a succession of
Carnot cycles.
therefore, what is true for a Carnot cycle is true of all
reversible cycles.
𝑑𝑄𝐿 𝑑𝑄𝐻
_ + =0
𝑇𝐿 𝑇𝐻

𝑑𝑄
_ ∆𝑆𝑐𝑦𝑐𝑙𝑒 = ර =0
𝑇

This means that entropy is a

state variable
 Entropy for Reversible Process
𝑆𝑖𝑛𝑐𝑒 𝑒𝑛𝑡𝑟𝑜𝑝𝑦 𝑖𝑠 𝑠𝑡𝑎𝑡𝑒 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛

𝑑𝑄
_ ∆𝑆𝑡𝑜𝑡𝑎𝑙 = න
𝑎𝐼𝑏 𝑇

𝑑𝑄
_∆𝑆𝑡𝑜𝑡𝑎𝑙 = න
𝑎𝐼𝐼𝑏 𝑇

If a process is adiabatic dQ = 0 & ∆𝐒𝐭𝐨𝐭𝐚𝐥 = 0 (Isentropic process)

 Mathematical Statement Of Second Law
❑ The total entropy of the universe increases whenever
an irreversible process occurs.
❑ The total entropy of the universe is unchanged
whenever a reversible process occurs.
∆𝑆𝑡𝑜𝑎𝑙 ≥ 0
second law of thermodynamics – the universe, or in any
isolated system, the degree of disorder (entropy) can
only increase.

Is it possible to decrease entropy of a system by any means?

If entropy decreases in a system due to work being done on
it, a greater increase in entropy occurs outside the system.
 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
𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 − 𝑑𝑊 _ 𝑑𝑈 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉
Enthalpy:
𝐻 = 𝑈 + 𝑃𝑉 _ 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃

_ 𝑑𝐻 = 𝑑𝑄𝑟𝑒𝑣 − 𝑃𝑑𝑉 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃

_ 𝑑𝑄𝑟𝑒𝑣 = 𝑑𝐻 − 𝑉𝑑𝑃
𝑅𝑇
For an ideal gas, 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 & 𝑉 =
𝑃

𝑑𝑄𝑟𝑒𝑣 𝑑𝑇 𝑑𝑃 𝑑𝑇 𝑑𝑃
= 𝐶𝑃 −𝑅 _ 𝑑𝑆 = 𝐶𝑃 𝑇 − 𝑅 𝑃
𝑇 𝑇 𝑃
𝑇2
𝑑𝑇 𝑃2
𝑑𝑃 𝑇2 𝑃2
∆𝑆 = න 𝐶𝑃 −න 𝑅 _ ∆𝑆 = 𝐶𝑃 𝑙𝑛 𝑇 − 𝑅𝑙𝑛 𝑃
𝑇1
𝑇 𝑃 1
𝑃 1 1
 Entropy Changes of an Ideal Gas
𝑇2 𝑃2
∆𝑆 = 𝐶𝑃 𝑙𝑛 − 𝑅𝑙𝑛
𝑇1 𝑃1

For isothermal process,

𝑃2
∆𝑆 = −𝑅𝑙𝑛
𝑃1
For ideal gas (at constant temperature):
𝑃2 𝑉1
𝑃1 𝑉1 = 𝑃2 𝑉2 _ =
𝑃1 𝑉2

𝑉1
_ ∆𝑆 = −𝑅𝑙𝑛
𝑉2
[Example] Calculate the entropy change when 1 kmol of
an ideal gas at 300 K and 10 bar expands through a
throttle to a pressure of 1 bar, both pressures being
maintained constant during the process by suitable
means
[Example] What is the change in entropy when 1 kmol of
an ideal gas at 335 K and 10 bar is expanded
irreversibly to 300 K and 1 bar? CP = 29.3 kJ kmol-1 K-1
 Entropy Changes of Adiabatic Mixing
Process
❑ When two substances at different temperatures are
mixed together adiabatically, both will attain an
intermediate temperature, say, T.

The change in entropy of each is calculated as

𝑇
𝑑𝑄𝑅 𝑑𝑇 𝑇
∆𝑆 = න = න 𝑚𝐶𝑃 = 𝑚𝐶𝑃 𝑙𝑛
𝑇 𝑇1 𝑇 𝑇1

where T1 denotes its initial temperature.

[Example] Ten kilograms water at 375 K is mixed adiabatically
with 30 kg water at 275 K. What is the change in entropy?
Assume that the specific heat of water is 4.2 kJ/kg K and is
independent of temperature
[Example] 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 (i) the casting, (ii) the oil, and (iii) both
considered together?
 Entropy and Irreversibility
❑ The total increase in entropy associated with an actual process
is a measure of the loss in capacity of the system and
surroundings as a whole to do work.
❑ In other words, the increase in entropy accompanying a
spontaneous process is a measure of lost work.
Consider an irreversible process in which a quantity of heat Q is transferred
from a source at a temperature TH to a sink at a lower temperature TL.
The change in total entropy in this process is given by
𝑄 𝑄 𝑇 − 𝑇𝐿
∆𝑆𝑡𝑜𝑡𝑎𝑙 = − _ ∆𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑄 𝐻
𝑇𝐿 𝑇𝐻 𝑇𝐻 𝑇𝐿
Now consider a reversible heat engine operating between the same thermal
reservoirs receiving the same quantity of heat Q.
The efficiency of such an engine is given by
𝑇𝐿
η=1− _ η = 𝑇𝐻 − 𝑇𝐿
𝑇𝐻 𝑇𝐻
 Entropy and Irreversibility
The work output of the engine (For Reversible Process)
𝑇𝐻 − 𝑇𝐿
W=𝑄
𝑇𝐻
This the work which would have resulted had the heat transfer process been
reversible, but which was lost because of the irreversible nature of the
process
𝑇𝐻 − 𝑇𝐿
W = 𝑄𝑇𝐿 _ 𝑊𝑙𝑜𝑠𝑡 = 𝑇𝐿 ∆𝑆 𝑇𝑜𝑡𝑎𝑙
𝑇𝐻 𝑇𝐿
❑ The product of total entropy change and the temperature of the heat sink gives
the quantity of heat that is wasted or degraded in an irreversible process.
❑ A reversible engine which receives heat QH from the reservoir at temperature
TH would perform some work rejecting a part of it, say QL, to a heat sink at
temperature TL. The heat rejected in the case of an irreversible engine which
receives the same amount of heat would be greater by an amount equal to
TL(ΔS)total.
❑ Thus TL(ΔS)total represents heat taken in at a higher temperature that would
have been available for doing work had the process been reversible, but that
was lost because of the irreversibility of the actual process.
 Entropy and Irreversibility
Though Equation is developed for a heat transfer process, it can be
shown that it is applicable to any process.
We can generalise the equation into the following form

𝑊𝑙𝑜𝑠𝑡 = 𝑇0 ∆𝑆 𝑇𝑜𝑡𝑎𝑙

T0 is the temperature of the surroundings.

❑ In practice, it is approximately equal to the temperature of the
atmosphere.
❑ The lower the value of T0, the lesser the work loss due to irreversibility
of the process. But, the lowest practicable temperature is that of the
atmosphere.
❑ To maintain the temperature of a heat sink below that of the
atmosphere, work is needed, and this work would be more than that is
gained by lowering T0.
[Example] Hydrocarbon oil is to be cooled from 425 K to 340 K at a
rate of 5000 kg/h in a parallel flow heat exchanger. Cooling water
at a rate of 10,000 kg/h at 295 K is available. The mean specific
heats of the oil and water are respectively 2.5 kJ/kg K and 4.2
kJ/kg K.
(a) Determine the total change in entropy. Is the process reversible?
(b) If a reversible Carnot engine is to be operated receiving the
heat from the oil and rejecting the heat to the surroundings at 295
K, how much work would be available?
 The Third Law of Thermodynamics
The absolute entropy is zero for a perfect crystalline
substance at absolute zero of temperature ( 0 K)

lim S = 0
T →0

▪ Absolute zero is a temperature that an object can

get arbitrarily close to, but never attain.
▪ Temperatures as low as 2.0 x 10-8 K have been
achieved in the laboratory, but absolute zero will
remain ever elusive – there is simply nowhere to “put”
that last little bit of energy.
 The Third Law of Thermodynamics
It is impossible to lower the temperature of an
object to absolute zero in a finite number of
steps.
▪ No system can reach absolute zero
▪ This is one reason we use the Kelvin
temperature scale. ( you never have to worry
about dividing by zero in an equation!)
 Practical uses: surroundings & system
Entropy Changes in Surroundings
❑ Heat that flows into or out of the system also
changes the entropy of the surroundings.

For an isothermal process:

−𝑞𝑠𝑦𝑠
∆𝑆𝑠𝑢𝑟𝑟 =
𝑇

At constant pressure, qsys is simply H for the system.

−𝑞𝑠𝑦𝑠 −∆𝐻
∆𝑆𝑠𝑢𝑟𝑟 = =
𝑇 𝑇
 S and H: Phase changes
−𝑞𝑠𝑦𝑠 −∆𝐻
∆𝑆𝑠𝑢𝑟𝑟 = =
𝑇 𝑇

For water:
Hfusion = 6 kJ/mol
Hvap = 41 kJ/mol

A phase change is isothermal (no change in T). If we do this reversibly:

Ssurr = –Ssys
 Calculation of Absolute entropy
Third law of thermodynamics can be utilized to
calculate the absolute entropy of substances
𝑇𝑓 𝑇𝑣 𝑇
𝐶𝑃,𝑆 𝑑𝑇 ∆𝐻𝑓 𝐶𝑃,𝐿 𝑑𝑇 ∆𝐻𝑣 𝐶𝑃,𝐺 𝑑𝑇
𝑆=න + +න + +න
0 𝑇 𝑇𝑓 𝑇𝑓 𝑇 𝑇𝑣 𝑇𝑣 𝑇

Where,
▪ CP,S, CP,L and CP,G are specific heat of solid, liquid and
gas respectively.
▪ ΔHf and ΔHv are the latent heats of fusion and
vaporization respectively
[Example] Calculate the absolute entropy of water vapour at 473 K
and 101.3 kPa above 273 K base temperature. Compare this with the
value reported in the steam tables (S = 7.829 kJ/kg K). The
average heat capacity of water is 4.2 kJ/kg K and that of water
vapour between 373 K and 473 K is 1.9 kJ/kg K. The latent heat of
vaporization at 373 K is 2257 kJ/kg.
 Entropy vs. Enthalpy
The enthalpy of a system is defined as:
H = U + PV
And the change in enthalpy, ΔH = ΔU + Δ(PV)

For constant pressure processes:

ΔH = ΔU +PΔV = ΔU +Work = Q!

❑ Enthalpy is sometimes described as the heat content

of a system under a given pressure

❑ Adding or removing energy through heat is the only

way to change the enthalpy.
 Entropy vs. Enthalpy

ENTHALPHY: Is the energy content of a

process that CAN be recovered.
▪ It is also described as useful energy.

ENTROPY: Is the energy content of a

process that CANNOT be recovered.
▪ It is also described as chaos.
 Unavailability of Energy; Heat Death
Entropy : a measure of the amount of energy which is
unavailable to do work

Another consequence of the second law:

❑ In any natural process, some energy becomes
unavailable to do useful work.
❑ If we look at the universe as a whole, it seems
inevitable that, as more and more energy is
converted to unavailable forms (continual increase
in entropy, the entire universe would have come
to the same temperature), the ability to do work
anywhere will gradually vanish. This is called the
heat death of the universe.