System

A system is defined as a quantity of matter or a region in space chosen for study.  The mass or
region outside the system is called the surroundings. 

Boundary: the real or imaginary surface that separates the system from its surroundings. The
boundaries of a system can be fixed or movable. Mathematically, the boundary has zero
thickness, no mass, and no volume.
Systems can be:
• Open: Mass and Energy can transfer between the System and the Surroundings
• Closed: Energy can transfer between the System and the Surroundings, but NOT mass
• Isolated: Neither Mass nor Energy can transfer between the System and the Surroundings

Properties of a System
Two classes of Properties:
• Extensive: Depend on the size of the system (n, m, V,…)
• Intensive: Independent of the size of the system (T, p, V = V ,…)
State and Equilibrium
At a given state, all the properties of a system have fixed values. Thus, if the value of even one
property changes, the state will change to different one.
In an equilibrium state, there are no unbalanced potentials (or driving forces) within the
system. A system in equilibrium experiences no changes when it is isolated from its
surroundings.  

 Thermal equilibrium: when the temperature is the same throughout the entire system.
 Mechanical equilibrium: when there is no change in pressure at any point of the system.
However, the pressure may vary within the system due to gravitational effects.

 Phase equilibrium: in a two phase system, when the mass of each phase reaches an
equilibrium level.  

 Chemical equilibrium: when the chemical composition of a system does not change with time,
i.e., no chemical reactions occur.
Processes, Paths and Cycles
Any change a system undergoes from one equilibrium state to another is called a process, and
the series of states through which a system passes during a process is called a path.
Adiabatic: no heat transfers from or to the fluid
Isothermal: no change in temperature of the fluid
Isobaric: no change in pressure of the fluid
Isochoric: no change in volume of the fluid
Isentropic: no change of entropy of the fluid
Isenthalpic: no change of enthalpy of the fluid
non-flow process
flow process
Quasi-static process
Reversible and Irreversible Processes
A process is reversible with respect to the system and surroundings if the system and the
surroundings can be restored to their respective initial states by reversing the direction of the
process, that is, by reversing the heat transfer and work transfer. The process is irreversible if it
cannot fulfill this criterion.

A system is said to have undergone a cycle if it returns to its initial state at the end of the
process.
Path function
A Path function is a function whose value depends on the path followed by a thermodynamic
process, and not on the initial and final states of the system.
An example of path function is work done in a thermodynamic process. Work done in a
thermodynamic process is dependent on the path followed by the process.
2
Thus ∫ δQ ≠Q 2 −Q 2and is shown as Q 1−2
1

Point function
A Point function is a function whose value depends on the final and initial states of the
thermodynamic process, irrespective of the path followed by the process.
2
 ∫ dV =V 2−V 1 (an exact differential)
1
Note: Since a point function is only dependent on the initial or final state of the system, hence in
a cyclic process value of a thermodynamic function is zero, or change in thermodynamic
property is zero. The operator δ is used to denote inexact differentials and operator dis used to
denote exact
differentials.
 2.0 Thermodynamics working fluids
Behavior of the working substance is very essential factor in understanding thermodynamics. In
this book, focus is given to pure substances such as gases and steam properties and how
they are interrelated are important in the design and operation of thermal systems.

2.1 The Ideal Gas

2.2Laws of Perfect Gases
1
Boyle's law: p ∝ ( T=C)
V
Charles' law: v ∝ T (P=C)
Gay-Lussac Law: p ∝ T (V=C)
Characteristic Equation of a Gas:
An ideal gas is governed by the perfect gas equation of state which relates the state
pressure (P), volume (V) and temperature (T) of a fixed mass (m is constant) of a given
gas (R is constant) as:

PV = mRT

The specific gas constant R, is a property related to the molar mass (M) in kg/kmol, of
the gas and the Universal gas constant Ro as

R = Ro / M
where Ro= 8314.3 J/kgK

2.2.1 Gas Equation During a Change of State

The equation of state can be used to determine the behaviour of the gas during a process,
i.e. what happens to its temperature, volume and pressure if any one property is
changed. This is defined by a simple expression relating the initial and final states such
as

P1V 1 P2V 2
=
T1 T2
2.3 Pure Substance
A pure substance is one, which is homogeneous and chemically stable. Thus it can be a single
substance which is present in more than one phase, for example liquid water and water vapour
contained in a boiler in the absence of any air or dissolved gases.
2.2.1 Phase -is the State of the substance such as solid, liquid or gas.
2.2.2 Mixed Phase- It is possible that phases may be mixed, e.g ice + water, water +
vapour etc.

2.2.3 Phase‐Change Processes of Pure Substances

a. Solid
b. Mixed phase of liquid and solid
c. Sub‐cooled or compressed liquid (A liquid that is not about to vaporize)
d. Saturated liquid (A liquid that is about to vaporize)
 e. Wet vapor or saturated liquid‐vapor mixture, the temperature will stop rising
until the liquid is completely vaporized
f. Superheated vapor (a vapor that is not about to condense)

**Degree of Superheat -The difference between the actual temperature of a given vapour and
the saturation temperature of the vapour at a given pressure.
**Degree of Subcool-The difference between the saturation temperature and the actual
temperature of the liquid is a given pressure.
2.2.4 Critical Point -A state point at which transitions between liquid and
vapour phases are not clear.

For H2O:
• PCR= 22.09 MPa
• TCR= 374.14oC (or 647.3 oK)
• VCR= 0.003155 m3/kg
 2.2.4 Triple Point -A state point in which all solid, liquid and vapour phases
coexist in equilibrium.

Water T = 0.01°C = 273.16 K and P = 0.6113 kPa

2.2.5 Quality of a Mixed Phase or Dryness Fraction (x)

The dryness fraction is defined as the ratio of the mass of pure vapour present to the
total mass of the mixture (liquid and vapour; say 0.9 dry for example). The quality of the
mixture may be defined as the percentage dryness of the mixture (ie, 90% dry).
If ms = Mass of dry steam contained in steam considered, and
mw = Weight of water particles in suspension in the steam
considered,
ms
Then, x=
ms +m m
3.0 Laws of Thermodynamics

3.1 Zeroth Law of Thermodynamics

The "zeroth law" states that if two systems are at the same time in thermal
equilibrium with a third system, they are in thermal equilibrium with each other.

If A and C are in thermal equilibrium with B, then A is in thermal equilibrium with B.

 Consequence of the zero’th law:
B acts like a thermometer, and A, B and C are all at the same “temperature”.

3.1.1 Temperature:
it can be defined as the degree of hotness or coldness.

being more precise-

Temperature is a measure of how hot or cold something is; specifically, a measure of
the average kinetic energy of the particles in an object, which is a type of energy
associated with motion. For instance, how hot is melted iron? To answer that question, a
physical scientist would measure the temperature of the liquid metal.

Heat
Heat (denoted by the symbol Q) is energy transferred between a system and its surroundings by
virtue of a temperature difference only.
Sign convention: If heat enters the system, then it is positive or if heat flows from the system,
then it is said to be negative.

Work
Work is said to be done when a force moves through a distance. If a part of the boundary of
a system undergoes a displacement under the action of a pressure, the work done W is the
product of the force (pressure × area), and the distance it moves in the direction of the force.

Let at any small section (shown shaded), the pressure (p) of the system is constant. If A is the
cross-sectional area of the piston, then force on the piston (F = pA) causes the piston to move
through a distance dx. Thus, work done by the system,
δW = Fdx = pAdx = pdv
Workdone for non-flow process from state I to state 2,
2 2
W = ∫ δW =∫ pdv
1 1
So the work done equals the area under a pV curve.
Sign convention: Thus we define work as being positive when the system does work on the
surroundings (energy leaves the system). If work is done on the system (energy added to the
system), the work is negative.

Comparison of Work and Heat

Heat is the transfer of thermal energy between systems, while work is the transfer of
mechanical energy between two systems.

Similarities:
(i) Both are path functions and inexact differentials.
(ii) Both are boundary phenomenon i.e.both are recognized at the boundaries of the
system as they cross them.
(iii) Both are associated with a process, not a state. Unlike properties, work or heat has
no
meaning at a state.
(iv) Systems possess energy, but not work or heat.

Dissimilarities:
(i) In heat transfer temperature difference is required.
(ii) In a stable system there cannot be work transfer, however, there is no restriction for
the transfer of heat.
(iii) The sole effect external to the system could be reduced to rise of a weight but in the
case of a heat transfer other effects are also observed.

Internal energy (U)

Internal energy is the energy stored within the object. It is difficult to state its absolute value.
For most processes this is not necessary because we would not be able to release or use it
completely, we are interested only in how much the internal energy has changed (∆U = UFINAL
− UINITIAL), if it has risen or decreased and which macroscopic quantities (p, V, T, ...) it
influenced.
Types of internal energy:
a) kinetic (Uk) – representing the chaotic movement of the particles, ∆U k ≈ ∆T
b) potential (Up) – representing the strength of bonds, ∆U ≈ change in strength of bonds (state of
matter)
c) energy of electrons in electron shells – can be changed when chemicals change, electrons
change the energy levels etc
d) nuclear – can be released when nucleus changes (fusion, fission, decay)

Specific Heat C
The specific heatof a solid or liquid is usually defined as the heat required to raise unit mass
through one-degree temperature rise.
For small quantities, we have
dQ= mcdT
Specific heat at constant volume, cv
and, Specific heat at constant pressure, c p
We have
dQ= m cpdT For a reversible non-flow process at constant pressure ...(4.16)
and, dQ= m cvd TFor a reversible non-flow process at constant volume
Relationship Between Two Specific Heats
Cp – C v = R

Ratio of Specific Heats

The ratio of specific heat at constant pressure to the specific heat at constant volume is
given the symbol γ(gamma).
Cp
i.e., γ=
Cv
Cp= Cv+ R, it is clear that Cp must be greater than Cv for any perfect gas. It follows,
therefore, that the ratio, γ is always greater than unity.
In general, the approximate values of γ are as follows :
For monoatomic gases such as argon, helium= 1.6.
For diatomic gases such as carbon monoxide, hydrogen, nitrogen and oxygen= 1.4.
For triatomic gases such as carbon dioxide and sulphur dioxide= 1.3.
For some hydro-carbons the value of γ is quite low e.g., for ethane γ= 1.22, and for
isobutane γ= 1.11

Enthalpy
— One of the fundamental quantities which occur invariably in thermodynamics is the
sum of internal energy (u) and pressure volume product (pv). This sum is called
Enthalpy(h).
i.e., h= u+ pv (4.24),
The total enthalpy of mass, m, of a fluid can be
H= U+ pV, where H= mh.
For a perfect gas,
Referring equation (4.24),
h= u+ pv
= cvT+ RT [ pv= RT]
= (cv+ R)T
= cpT [ cp= cv+ R]
i.e., h= cpT
and H= mcpT.

The first law of thermodynamics

When a process is executed by a system, the change in stored energy of the system is
numerically equal to the net heat interactions minus the net work interaction during the
process
ΔU = Q – W
Remember:
Qin is positive - W done by the system is positive
Qout is negative - W done on the system is negative

Joule’s Law
“The internal energy of a perfect gas is a function of the absolute temperature only.”
i.e., u= f(T)
To evaluate this function let 1 kg of a perfect gas be heated at constant volume.
According to non-flow energy equation,
dQ= du+ dW
dW= 0, since volume remains constant
∴ dQ= du
At constant volume for a perfect gas, from eqn. (4.17), for 1 kg
dQ= cvdT
∴ dQ= du= cvdT
For mass m, of a perfect gas
Internal energy, U= mcvT

Corollaries of the First Law

A. Work done in any adiabatic (Q=0) process is path independent

B. For a cyclic process heat and work transfers are numerically equal

Limitations of First Law of Thermodynamics

We have already discussed that according to first law of thermodynamics that
-
1.When a closed system undergoes a thermodynamic cycle, the net heat transfer is equal
to the net work transfer. This statement does-not specify the direction of flow of heat and
work (i.e.whether the heat flows from a hot body to a cold body or from a cold body to a
hot body). It also does not give any condition under which these transfers take place.
2.The heat energy and mechanical work are mutually convertible.
Though the mechanical work can be fully converted into heat energy, but only a part of
heat energy can be converted into mechanical work. This means that the heat energy and
mechanical work are not fully mutually convertible. In other words, there is a limitation
on the conversion of one form of energy into another form.

PERPETUAL MOTION MACHINE OF THE FIRST KIND—PMM 1

A machine which violates the first law of thermodynamics (i.e. energy can neither be
created nor destroyed, but can be transformed from one form to another) is known as
perpetual motion machine of the first kind (briefly written as PMM-I). It is defined as
a machine which produces work energy without consuming an equivalent of energy from
other source.
APPLICATION OF FIRST LAW OF THERMODYNAMICS TO NON-FLOW OR
CLOSED SYSTEM

Summary of Processes for Perfect Gas

Reversible Inde p-v-T Workdone Chang Heat supplied Chang Specif
non-flow xn relatio W1-2 e of Q1-2 = dU+ W1-2 e in ic
process n intern enthal heat,
al py c
Energ dH
y
dU
Constant n= T1 P1 0 mcv mcv (T2-T1) mcp(T2 cv
Volume ∞ = (T 2-T1) -T1)
T P 2 2
Constant n= 0 T 1 v1 p(v2– v1) mcv(T2 mcp(T2-T1) mcp(T2 cp
Pressure = -T1) -T1)=
T 2 v2
Q1-2
Constant n=1 p1v1= v2 0 v2 0 ∞
Temperature p2v2 p1v1ln( ) p1v1ln( )
v1 v1
Reversible n= γ p1v1γ= v1−¿ p v mcv 0 mcp(T2 0
Adiabatic p2v2γ p1 2
¿ (T2-T1)2
-T1)
γ −1
T 2 V 2 γ −1 Or
=( )
T 1 V 2 mR (T 2−T 1)¿ ¿
= γ −1
P2 γ −1
( ) γ
P1

Polytropic n=n γ=n γ=n mcv γ −n mR (T 2−T 1) mcp(T2 cn= cv(

(T2-T1) x -T1) γ −n
γ −1 γ−1 ¿
1−n
Free 0 0 0 0
Expansion(dT U1=U2 H1=H2
=0)
APPLICATION OF FIRST LAW TO STEADY FLOW PROCESS OR
OPEN SYSTEM
The first law of thermodynamics is based on the conversation of energy within a system. Open
systems are associated with those, which have a steady flow, thus the first law applied to such
systems is known as the Steady Flow Energy Equation (SFEE):
Q-W = (∆H+ ∆KE+ ∆PE) = m[(h2-h1)+1/2(V 22−V 21 )+g(Z2-Z1)]
Assumptions:
The following assumptions are made in the system analysis:
(i) The mass flow through the system remains constant.
(ii) Fluid is uniform in composition.
(iii) The only interaction between the system and surroundings are work and heat.
(iv) The state of fluid at any point remains constant with time.
(v) In the analysis only potential, kinetic and flow energies are considered.
Devices Conditions SFEE
ṁ 1=ṁ 2 h1-h2=1/2(V 22−V 21 )
∆PE=0
W=0
Q=0

Nozzles
Diffusers ṁ 1=ṁ 2 h2-h1=1/2(V 21−V 22 )
∆PE=0
W=0
Q=0

Turbines ṁ 1=ṁ 2 W=ṁ (h1-h2)

∆PE=0
Q=0

Compressors ṁ 1=ṁ 2 W=ṁ (h2-h1)

∆PE=0
Q=0

Throttling ṁ1=ṁ2 h1=h2

∆PE=0
∆KE=0
W=0
Q=0

Mixing Chambers ṁ 1+ṁ 2 =ṁ 3 ṁ 1h1+ṁ 2 h2=(ṁ 1+ṁ 2) h3

∆PE=0
∆KE=0
W=0
Q=0(if well-insulated)

Heat Exchangers ṁ A1=ṁ A2=ṁ A ṁ A(hA1- hA2) = ṁ B(hB2-

 ṁ B1=ṁ B2=ṁ B hB1)
∆PE=0
∆KE=0
W=0
Q=0(if well-insulated)

Boilers ṁ1=ṁ2 Q=(h2-h1)

∆PE=0
W=0

Condensers ṁ 1=ṁ 2 Q=(h1-h2)

∆PE=0
W=0

Evaporators ṁ1=ṁ2 Q=(h2-h1)

∆PE=0
W=0

The Second Law of Thermodynamics

The second law of thermodynamics states that processes occur in a certain direction, not in just any
direction.
Physical processes in nature can proceed toward equilibrium spontaneously. For examples
Water always flows downhill

Heat always flows from high temperature to low temperature

Can We Take Advantage of These Processes?

• Yes!! We can use them to produce work

• Or… we can just let them happen and lose the opportunity.

Can we reverse these processes?

• It requires the expenditure of work

• The first law gives us no information about the direction in which a process occurs – it only tells us that
energy must balance

• The second law tells us what direction processes occur

Thermal Energy Reservoirs

Thermal energy reservoirs are hypothetical bodies 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.  Lakes, rivers, atmosphere, oceans are example of thermal reservoirs.  

A two‐phase system can be modeled as a reservoir since it can absorb and release large quantities of
heat while remaining at constant temperature.

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.

Heat Engines

Heat engines convert heat to work. There are several types of heat engines, but they are characterized
by the following:

1‐ They all receive heat from a high‐temperature source (oil furnace, nuclear reactor, etc.)  

2‐ They convert part of this heat to work

3‐ They reject the remaining waste heat to a low‐temperature sink

4‐ They operate in a cycle.

Thermal efficiency: is the fraction of the heat input that is converted to the network output (efficiency =
benefit / cost).  
The thermal efficiencies of work‐producing devices are low. Ordinary spark‐ignition automobile engines
have a thermal efficiency of about 20%, diesel engines about 30%, and power plants in the order of 40%.

Is it possible to save the rejected heat Q out in a power cycle?

The answer is NO, because without the cooling in condenser the cycle cannot be completed. Every heat
engine must waste some energy by transferring it to a low‐temperature reservoir in order to complete
the cycle, even in idealized cycle.

The Second Law: 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. In other words, no heat engine
can have a thermal efficiency of 100%.  

Refrigerators and Heat Pumps

In nature, heat flows from high‐temperature regions to low‐temperature ones. The reverse process,
however, cannot occur by itself. The transfer of heat from a low‐ temperature region to a high‐
temperature one requires special devices called refrigerators. Refrigerators are cyclic devices, and the
working fluids used in the cycles are called refrigerant.  

Heat pumps transfer heat from a low‐temperature medium to a high‐temperature one. Refrigerators
and heat pumps are essentially the same devices; they differ in their objectives only. Refrigerator is to
maintain the refrigerated space at a low temperature. On the other hand, a heat pump absorbs heat
from a low‐temperature source and supplies the heat to a warmer medium.  
Coefficient of Performance (COP)

The performance of refrigerators and heat pumps is expressed in terms of the coefficient of
performance (COP) which is defined as

It can be seen that COPHP = COPR + 1

Air conditioners are basically refrigerators whose refrigerated space is a room or a building.

The Energy Efficiency Rating (EER): is the amount of heat removed from the cooled space in BTU’s for 1
Wh (watt‐hour)  

EER = 3.412 COPR

Most air conditioners have an EER between 8 to 12 (COP of 2.3 to 3.5).

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 higher‐temperature body. In other words, a refrigerator will not operate unless its compressor
is driven by an external power source.

So What is the Best You Can Do?

• We know that Coefficients of Performance for refrigerators and heat pumps must be less than infinity,
but how much less?

• We know that thermal efficiencies for heat engines must be less than 100%, but how much less?

It Depends on… Irreversibility

Reversible and Irreversible Process

A reversible process is defined as a process that can be reversed without leaving any trace on the
surroundings. It means both system and surroundings are returned to their initial states at the end of
the reverse process. Processes that are not reversible are called irreversible.

Reversible processes do not occur and they are only idealizations of actual processes. We use reversible
process concept because, a) they are easy to analyze (since system passes through a series of
equilibrium states); b) they serve as limits (idealized models) to which the actual processes can be
compared.

Some factors that cause a process to become irreversible:

• Friction

• Unrestrained expansion and compression

• mixing

• Heat transfer (finite ∆T)

• Inelastic deformation

• Chemical reactions

In a reversible process things happen very slowly, without any resisting force, without any space
limitation → everything happens in a highly organized way (it is not physically possible ‐ it is an
idealization).  

Internally reversible process: if no irreversibility occurs within the boundaries of the system. In these
processes a system undergoes through a series of equilibrium states, and when the process is reversed,
the system passes through exactly the same equilibrium states while returning to its initial state.

Externally reversible process: if no irreversibility occurs outside the system boundaries during the
process. Heat transfer between a reservoir and a system is an externally reversible process if the surface
of contact between the system and reservoir is at the same temperature.

Totally reversible (reversible): both externally and internally reversible processes.

Reversible processes represent the best that we can do.

The Carnot Cycle

The efficiency of a heat‐engine cycle greatly depends on how the individual processes that make up the
cycle are executed.  The network (or efficiency) can be maximized by using reversible processes.  The
best known reversible cycle is the Carnot cycle composed of four reversible processes – 2 adiabatic heat
transfer – 2 reversible isothermal heat transfer,

Note that the reversible cycles cannot be achieved in practice because of irreversibility associated with
real processes. But, the reversible cycles provide upper limits on the performance of real cycles.
The Carnot principles state that the thermal efficiencies of all reversible heat engines
operating between the same two reservoirs are the same, and that no heat engine
is more efficient than a reversible one operating between the same two
reservoirs.

• These statements form the basis for establishing a thermodynamic

temperature scale related to the heat transfers between a reversible
device and the high- and low-temperature reservoirs by
The energy has quality as well as quantity

The second law of thermodynamics asserts that processes occur in a certain direction and that the
energy has quality as well as quantity.

Consider a Carnot heat engine working between two thermal reservoirs T L = 300 K and TH. The thermal
efficiency of the heat engine increases as the heat source temperature T H is increased.

The thermal efficiency of actual heat engine can be maximized by supplying heat to the engine at the
highest possible temperature (limited by material strength) and rejecting heat to lowest possible
temperature (limited by the cooling medium temperature such as atmosphere, lake, river temperature).

From the above table, it can also be seen that the energy has a quality. More of the high‐ temperature
thermal energy can be converted to work. Therefore, the higher the temperature, the higher the quality
of the energy will be. 

The Carnot Refrigeration and Heat Pump Cycle A refrigerator or heat pump that operates on the reverse
Carnot cycle is called a Carnot Refrigerator, or a Carnot heat pump.  

The Coefficient of performance of any refrigerator or heat pump (reversible or irreversible) is given by:

Reversible and Real Systems Comparison

• The efficiency of a reversible heat engine, such as a Carnot engine, is always higher than a real engine
• The COP of a reversible heat pump is always higher than a real heat pump

• The COP of a reversible refrigerator is always higher than a real refrigerator

Entropy and the Second Law of Thermodynamics: Disorder and the Unavailability of Energy
There is yet another way of expressing the second law of thermodynamics. This version relates to

a concept called entropy. By examining it, we shall see that the directions associated with the

second law—heat transfer from hot to cold, for example—are related to the tendency in nature for

systems to become disordered and for less energy to be available for use as work. The entropy of

a system can in fact be shown to be a measure of its disorder and of the unavailability of energy to

do work.

Making Connections: Entropy , Energy , and W ork

Recall that the simple definition of energy is the ability to do work. Entropy is a measure of

how much energy is not available to do work. Although all forms of energy are

interconvertible, and all can be used to do work, it is not always possible, even in principle,

to convert the entire available energy into work. That unavailable energy is of interest in

thermodynamics, because the field of thermodynamics arose from efforts to convert heat to

work.

We can see how entropy is defined by recalling our discussion of the Carnot engine. We noted

that for a Carnot cycle, and hence for any reversible processes, Q H/QL = TH/TL . Rearranging

terms yields

QH/TH = QL/TL

This ratio of Q/T is defined to be the change in entropy ΔS for a reversible process,

Q
ΔS = ( ¿rev
T
where Q is the heat transfer, which is positive for heat transfer into and negative for heat transfer

out of, and T is the absolute temperature at which the reversible process takes place. The SI unit

for entropy is joules per kelvin (J/K).

Now let us take a look at the change in entropy of a Carnot engine and its heat reservoirs for one full
QH
cycle. The high temperature reservoir has a loss of entropy ΔSH = - , because heat transfer occurs
TH
out of it (remember that when heat transfers out, then Q has a negative sign). The low
QL
temperature reservoir has a gain of entropy ΔSL = , because heat transfer occurs into it. (We
TL
assume the reservoirs are sufficiently large that their temperatures are constant.) So the total
change in entropy is
ΔStot = ΔSH + ΔSL
Thus, since we know that QH/TH = QL/TL for a Carnot engine,
QH QL δQ
ΔStot = - + = 0 i.e for a reversible cyclic ∑ =0.
TH TL cycle T

Entropy and the Unavailability of Energy to Do Work

What does a change in entropy mean, and why should we be interested in it? One reason
is that entropy is directly related to the fact that not all heat transfer can be converted
into work. The below example gives some indication of how an increase in entropy
results in less heat transfer into work.

Less Work is Produced by a Given Heat Transfer When Entropy Change is Greater
(a) Calculate the work output of a Carnot engine operating between temperatures of 600 K and 100 K
for 4000 J of heat transfer to the engine. (b) Now suppose that the 4000 J of heat transfer occurs first
from the 600 K reservoir to a 250 K reservoir (without doing any work, and this produces the increase in
entropy calculated above) before transferring into a Carnot engine operating between 250 K and 100 K.
What work output is produced?
Solution (a)
The Carnot efficiency is given by
ηc = 1 – TL/TH = 1 – 100/600 = 0.833
again η = W/QH
W = η x QH = 0.833 x 4000 = 3333 j
Solution (b)
Similarly,
η'c = 1 – TL/TH = 1 – 100/250 = 0.600
W = η'c x QH = 0.600 x 4000 = 2400 j
Discussion
There is 933 J less work from the same heat transfer in the second process. This result is
important. The same heat transfer into two perfect engines produces different work
outputs, because the entropy change differs in the two cases. In the second case, entropy
is greater and less work is produced. Entropy is associated with the unavailability of
energy to do work.
(a) A Carnot engine working at between 600 K and 100 K has 4000 J of heat transfer and
performs 3333 J of work. (b) The 4000 J of heat transfer occurs first irreversibly to a 250 K
reservoir and then goes into a Carnot engine. The increase in entropy caused by the heat
transfer to a colder reservoir results in a smaller work output of 2400 J. There is a
permanent loss of 933 J of energy for the purpose of doing work.

When entropy increases, a certain amount of energy

becomes permanently unavailable to do work. The energy is not lost, but its
character is changed, so that some of it can never be converted to doing work
—that is, to an organized force acting through a distance. 

Now the increase in entropy for the system of two heat reservoirs

undergoing this irreversible heat transfer is

QH
ΔSH = - = -4000/600 = -6.67 j/k
TH
 QL
ΔSL = = 4000/250 = 16 j/k
TL
ΔStot = ΔSH + ΔSL = -6.67 + 16 = 9.33 j/k

For instance, in the previous example, 933 J less work was done after an increase in
entropy of 9.33 J/K occurred in the 4000 J heat transfer from the 600 K reservoir to the
250 K reservoir. It can be shown that the amount of energy that becomes unavailable for
work is

Wunavail = ΔS x T0 where T0 is the lowest temperature utilized. In this example,

Wunavail = 9.33 x 100 = 933 j

as found.

Order to Disorder
Entropy is related not only to the unavailability of energy to do work—it is also a
measure of disorder. This notion was initially postulated by Ludwig Boltzmann in the
1800s. For example, melting a block of ice means taking a highly structured and orderly
system of water molecules and converting it into a disorderly liquid in which molecules
have no fixed positions.

There is a large increase in entropy in the process, as seen in the following example.

Entropy Associated with Disorder

Find the increase in entropy of 1.00 kg of ice originally at 0oC that is melted to form
water at 0oC.
Strategy
As before, the change in entropy can be calculated from the definition of ΔS once we find
the energy Q needed to melt the ice.
The change in entropy is defined as:
Q
ΔS =
T
Here Q is the heat transfer necessary to melt 1.00 kg of ice and is given by
Q = mLf
where m is the mass and Lf is the latent heat of fusion. Lf = 334 kj/kg for water, so that
Q = 1 x 334 = 334 kj
Now the change in entropy is positive, since heat transfer occurs into the ice to cause
the phase change; thus,
ΔS = 334/273 = 1.22 kj/k
Discussion
This is a significant increase in entropy accompanying an increase in disorder.