1

Chapter 2 Basic of Concepts of Thermodynamics

Thermodynamics
z It is defined as the science of energy and entropy.
z It is the science that deals with heat and work and those properties of
substances that bear a relation to heat and work.
z The first law of thermodynamics
z The second law of thermodynamics
z Classical thermodynamics
z Statistical thermodynamics
Dimensions and Units
z Mass
1lbm=0.45359kg
1slug=32.174lbm
z Length
1cm=0.3937in
1in=2.54cm
1ft=30.48cm
z Force
1N=1kgm/s 2 =10 5 Dyne
1lbf=32.174lbmft/s 2
z SI Unit Prefixes
10 12 T (tera) 10 3 m(milli)
10 9 G(giga) 10 6 (micro)
10 6 M(mega) 10 9 n(nano)
10 3 K(kilo) 10 12 p(pico)
z Volume
1l=10 3 m 3 =0.2642gal
z Energy
1BTU=778.16 ft-lbf=1055J
1cal=4.1855J
z Power
1HP=745.7w=550ft-lbf/s
z Specific VolumeThe specific volume of a substance is defined as the
volume per unit mass.
V
= (m 3 /kg)
m
1 m
z Density = = (kg/m 3 )
V

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Closed and open system

z Closed systemIt is defined as a quantity of matter of fixed mass and
identity on which attention if focused for study.
z Open system (Control Volume)It is a volume in space for a particular
study or analysis. Mass, heat, and work can cross the system surface.
z SurroundingsThe mass or region outside the system is called the
surrounding.
z BoundaryThe real or imaginary surface that separates the system from its
surroundings is called the boundary.
Forms of Energy
z Total energy E
z Kinetic energy KE
z Potential energy PE
z Internal energy U
Properties of a system
z PropertyAny characteristic of a system is called a property
z Intensive propertiesintensive properties are independent of the size of
system, such as temperature, pressure, and density.
z Extensive propertiesAn extensive property is one that depends on the size
or extent of the system, such as mass volume, and total energy.
State and Equilibrium
z StateA system does not undergo any change and all the properties can be
measured or calculated throughout the entire system, which gives us a set of
properties that completely describe the condition.
z The state of a system that may be identified by temperature, pressure, or
density. (the thermal properties)
z PhaseA phase is defined as a quantity of matter that is homogeneous
throughout. A substance has three different phases, liquid, vapor, and solid.
z EquilibriumIn a system, the value of the properties has significance for
the entire system that the system is called in equilibrium.
z The state postulateThe state of a simple compressible system is
completely specified by two independent, intensive properties.
Processes and Cycles
z ProcessWhen a system undergoes a change in state. The path of the
succession of states through which the system passes is called the process.
z Quasi-equilibrium processA quasi-equilibrium process is one in which the
deviation from thermodynamic equilibrium is infinitesimal. The process can
be viewed as a sufficiently slow process that allows the system to adjust

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itself internally so that properties in one part of the system do not change
any faster than those at other parts.
z All the states the system passes through during a quasi-equilibrium process
may be considered as an equilibrium process.
z The prefix iso is used to describe that one property remains constant.
Isothermal processconstant temperature process
Isobaric processconstant pressure process
Isochoric processconstant volume process
z CyclesWhen a system in a given initial state go through a number of
different changes of state or process and finally returns to its initial state, the
system has undergone a cycle.
Pressure
z Pressure is the force exerted by a fluid per unit area.
z The pressure in fluid at rest at a given point is the same in all direction, and
we define pressure as the normal component of force per unit area.
F
P= N/m 2
A
1Pa=1 N/m 2
1bar=10 5 Pa=0.1Mpa
1atm=101325Pa=14.696lbf/in 2
z Absolute pressure = gage pressure + atmospheric pressure
z Atmospheric pressure
z Gage pressure
z Vacuum pressure
z From the principles of hydrostatics one concludes that for a difference in
level of L meters, the pressure difference in pascals is calculated by the
relation
p = Lg Where is the density of the fluid, g=9.8m/s 2
The zeroth law of thermodynamics
When two bodies have equality of temperature with a third body, they in turn have
equality of temperature with each other.
Temperature scales
The temperature of the ice point and the steam point in equilibrium at a pressure
of 1 atm are numbered 0 and 100 on the Celsius scale.
0 90 0
F=32+ C R= 0 F+459.69
5
0 9
R= K K= 0 C+273.15
5

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Chapter 3 Properties of Pure Substances

Pure substance
A pure substance is one that has a homogeneous and invariable chemical
composition
Phase-change processes of pure substance
Consider the system that the water contained in the piston cylinder arrangement:
The saturation temperature designates the temperature at which vaporization takes
place at the saturation pressure.
T-V diagram:
Saturated vaporA vapor that is about to condense is called a saturated vapor.
Superheated vaporWhen the vapor is at a temperature greater than the saturation
temperature, it is said to exist as superheated vapor.
Saturated liquidA liquid that is about to vaporize is called a saturated liquid.
Subcooled liquidIf the temperature of the liquid is lower than the saturation
temperature for the existing pressure, it is called either a subcooled liquid or a
compressed liquid.
The critical pointFor water, at a pressure of 22.09Mpa and temperature 374.14
0
C, there is no constant temperature vaporization process. Instead, is a point of
inflection with a zero slope. This point is called the critical point and at the
critical point the saturated liquid and saturated vapor states are identical.
Substance critical temperature critical pressure critical volume
0
Water 374.14 C 22.09Mpa 0.003155m 3 /kg
CO 2 31.05 7.39 0.002
O2 -118.35 5.08 0.002
H2 -239.85 1.30 0.032192
z Latent heatA substance changing phase in a given pressure, the amount of
heat transfer is equal to the difference of the enthalpy of the two saturated
phases. The difference of the enthalpy is called the latent heat of the two
phases.

The latent heat of vaporization h fg

= hg h f

The latent heat of fusion h

if
= h f hi

The latent heat of sublimation hig

= h g hi

Saturated liquid line and saturated vapor lineThe saturated liquid line states in
T-V diagram can be connected by a line called the saturated liquid line, and
saturated states in the same diagram can be connected by another line, called

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the saturated vapor line.

P-V diagram:
T-V diagram:
Triple lineOn P-V or T-V diagrams, these triple-phase states form a line called
the triple line.
z Triple pointIt is the point that the three phases may exist together in
equilibrium.
P-T diagram:
P-V-T surface:
Vapor pressure
z Atmospheric air can be viewed as a mixture of dry air and water vapor, and the
atmospheric pressure is the sum of the pressure of dry air and the pressure of

water vapor. p = p +p
atm a v

z Relative humidityAir can hold a certain amount of moisture only, and the
ratio of the actual amount of moisture in the air at a given temperature to the
maximum amount air can hold at that temperature is called relative humidity.

m p
= v
= v
,and p = p
m g p
g
v g

Tables of thermodynamics
Internal energyIn the study of thermodynamics it is convenient to consider the
bulk kinetic and potential energy separately and then to consider all other
energy of the system in a single property that we call the internal energy, u
Internal energy is an extensive property, since it depends on the mass of the system.
u represents internal energy per unit mass and U represents the total internal
energy.
Enthalpy H=U+PV or, per unit mass h=u+pv.
Steam tables
Saturated steam tablesTemperature table A-4 and pressure table A-5
Superheated vapor tableA-6
Compressed liquid tableA-7
Saturated solid-vapor tableA-8
Saturated liquid-vapor mixture region
z In the two phases region, we need to know the proportions of the liquid and
vapor phases in the mixture. This is done by defining a new property called the
quality x as the ratio of the mass of vapor to the total mass of the mixture. x =

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m v
If x represents the quality of vapor then 1-x represents the quality of liquid.
m t

Therefore, in the liquid-vapor region, the mixing specific volume can be written:

v = (1-x)v f + x v g and v fg = v g -v f Then, v = v f + x v fg

Similarly, the internal energy u and the enthalpy h in the liquid-vapor region can be
written:

u = u f + x u fg , and h = h f + x h fg

Problems
120 0 C, 150KPa 0.35Mpa, 0.4m 3 /Kg
160 0 C, 0.4 m 3 /Kg 200KPa, 110 0 C
300 0 C, 0.01 m 3 /Kg 5KPa, 10 0 C
Ideal gas
Equations of state for ideal gas
R
Pv =RT or P v = R T where P(KPa), v(m 3 /Kg), R= , R = 8.3143
M
KJ/Kmole K, M is the molar mass, T(K)
PV = n R T where P(KPa), V(m 3 ), n is the mole number, R =
8.3143 KJ/Kmole K, T( K)
R
PV = mRT where P(KPa), V(m 3 ), m(Kg), R= , T( K)
M

Boyles and Charles law PV2 2

= PV
1 1

T 2 T 1

Real gas
Equations of state for real gas

a
Van der Waals equation of state P + 2 (

)
v b = RT
where a and b are
v

constants for different gas, P (KPa), v = Mv is the mole specific volume,

R = 8.3144KJ/KmoleK, T ( K)
a b
air 135.8 0.0364
CO 2 364.3 0.0407
CO 146.3 0.0394
O2 136.9 0.0315

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The determination of the two constants appearing in this equation is

based on the observation that the critical isotherm on the P-V diagram has a
horizontal inflection point at the critical point. Thus, the first and the second
derivatives of P with respect to V at the critical point must be zero. That is,

P 2P 27 R 2Tcr
2
RTcr

= 0 and 2 = 0, a = and b =
v T =Tcr =const v T =Tcr =const 64 Pcr 8Pcr

Beattie-Brdgeman equation of state

P=
RT
2
c
(
1 3 v + B 2 ) A a
Where A = A0 1 and
v vT v v
b
B = B0 1 A0 , a , B0 , b , and c are constants for different gases.
v
Benedict-Webb-Rubin equation of state

RT C 1 b RT a a c 2
P= + B0 RT A0 02 2 + + 6 + 3 1 + 2 v
v T v 3
v v v T2 v

Viral equation of state

RT a(T ) b(T ) c(T )
P= + 2 + 3 + 4 +
v v v v
Where a(T ) , b(T ) , c(T ) are viral coefficients and are functions of
temperature.
Compressibility factor Z
Pv
The definition of the compressibility factor is Z =
RT
Pv
For ideal gas Z= =1
RT
For the nitrogen:
The generalized compressibility factor
The definition of reduced coordinates
P
Reduced pressure PR =
Pcr
T
Reduced temperature TR =
Tcr
v
Reduced specific volume vR =
v cr
Pv
PR , TR Z Z =
RT

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Chapter 4: The first law of thermodynamics: Closed systems

Heat
HeatIt is defined as the form of energy that is transferred between two systems by
2
virtue of a temperature difference. Q12 = Q12
1

Heat transferred to a system is considered to be positive, heat transferred from a

system is negative.
A process during which there is no heat transfer is called an adiabatic process.
The amount of heat transfer when a system undergoes a change of state from state 1 to
state 2 depends on the path that the system follows during the change of state.
Modes of heat transfer
dT
ConductionThe Fouriers law of heat conduction Q cond = k t A (W)
dx
Where k t is the thermal conductivity of the material.

ConvectionThe Newtons law of cooling Q conv = hA(Ts T f ) (W)

Where h is the convection heat transfer coefficient

Forced convection
Free(or natural) convection

RadiationThe Stefan-Boltzmann law Q emit ,max = ATs4 (W)

Where = 5.67x10 8 W/m 2 K 4 is the Stefan-Boltzmann constant.

Blackbody

The radiation emitted by all real surface: Q emit = ATs4 (W)

Where is the emissivity of the surface.

Absorptivity, 0 1
The rate at which a surface absorbs radiation is determined from

Q abs = Q inc

Kirchhoffs lawThe emissivity and absorptivity of a surface are equal at

the same temperature and wavelength.
The net rate of radiation heat transfer between two surfaces is determined

from Q rad = A(Ts4 Tsurr
4
)

Work
Definition of workWork is the energy transfer associated with force acting

through a distance. W = F ds

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Work is done by the moving boundary of a simple compressible system in a

quasi-equilibrium process.
dV
F = PA , ds =
A
dV
W = F ds = PA = P dV
A
2 v2
W12 = W = PdV
1 v1

The work is represented by the area that is under the curve1-2, area
a-1-2-b-a.
The amount of work involved in each case is a function not only of the
end states of the process, but in addition is dependent on the path that
is followed in going from one state to another.
The work done on the system is considered to be negative, the work
done by the system is positive.
Polytropic processDuring expansion and compression processes of
real gases, pressure and volume are often related by PV n = C ,
where n is the polytropic exponent and C is a constant. For ideal
gases Pv = RT , therefore, n=1 is the constant temperature process,
n=0 is the constant pressure process, n= is the constant volume
1
v P1 n
process. Polytropic process relations: P v = P v , 2 n
2 2
n
1 1
= ,
v1 P2

n 1 n 1
T2 v1 T P2 n
= , 2 = , and work
T1 v2 T1 P1
2 2 P2V2 P1V1 mR(T2 T1 )
W = PdV = CV n dV = = ,n 1
1 1 1 n 1 n

z Gravitational work F = mg , W g = mg ( z 2 z1 )

1
Acceleration work F = ma , Wa = m(v22 v1 )
2
z
2
z Shaft work = Fr , Wsh = 2n
1
z Spring work F = kx , Wspring = k ( x 22 x12 )
2
The first law of thermodynamics

The first law of thermodynamics for a system undergoing a cycle: J Q = W ,

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 10

where J is a proportionality factor. In the SI units, the J equals to 1, and we

may rewrite as Q = W .
The first law of thermodynamics for a change in state of a system:

From the first law of thermodynamics of a cycle Q = W

Considering the two separate processes, we have
2 1 2 1
1
Q A + Q B = W A + W B
2 1 2

2 1 2 1
Now, consider another cycle
1
Q A + QC = W A + WC
2 1 2

Subtracting the second of these equations from the first, we

1 1 1 1
have QB QC = WB WC , or by rearranging
2 2 2 2

1 1
(Q W )
2
B = (Q W )
2 C

Since processes B and C represent arbitrary processes between states 1 and 2, we

conclude the quantity (Q W ) is the same for all processes between state
1 and state 2.
By introducing a new property, the energy, E : Q W = dE
Integrating from an initial state 1 to final state 2 Q12 = E 2 E1 + W12
The conservation of energy principleThe net change in the total energy of the
system during a process is equal to the difference between the total energy
entering and the total energy leaving the system during that process.

E in E out = E system

Ein = Qin Win , E out = Qout Wout , and E = U + KE + PE , where

1
U = m(u 2 u1 ) , KE = m(v 2 v12 ) , and PE = mg ( z 2 z1 )
2

2
The first law of thermodynamics : Closed systems
1
Q12 = m(u 2 u1 ) + m(v 22 v12 ) + mg ( z 2 z1 ) + W12
2
Specific heats
For a system, the amount of heat transfer may be considered as being proportional to
the different states. We will then define a variable termed the specific heat, the
amount of heat required per unit mass to raise the temperature by one degree.
q = cT Where c is the specific heat.
The constant volume specific heat cv

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 11

The constant volume process V = C , dV = 0

Q = dU + W = dU + PdV = mcv T
1 Q 1 U u
cv = = =
m T v m T v T v

The constant pressure specific heat c p

The constant pressure process P = C , Q = dU + PdV = dH = mc p T

1 Q 1 H h
cp = = =
m T p m T p T p
Internal energy, enthalpy, and specific heats of ideal gases
For ideal gas, the internal energy u and enthalpy h are only function of temperature.

Therefore: u = u (T ), h = h(T ) , du = c v (T ) dT , dh = c p (T ) dT ,

2 2
u = u 2 u1 = cv (T )dT , h = h2 h1 = c p (T )dT
1 1

Specific heat relation of ideal gases: dh du = (c p c v )dT , h = u + pv ,

dh = du + d ( pv ) = du + RdT , dh du = RdT , R = c p c v , and R = c p c v

Specific heat ratio : For adiabatic process Q = 0 , q = du + w = cv dT + Pdv ,

0 = c v dT + Pdv , c v dT = Pdv , Q h = u + Pv, dh = du + Pdv + vdP = c p dT ,

cp vdP dP c p dv cp
= , + = 0 , Pv = C , where = is the isentropic
cv Pdv P cv v cv
R R
exponent. But R = c p c v = ( 1)c v , cv = , cp =
1 1
Polytropic specific heat cn :
mR
Q = dU + W = mcv (T2 T1 ) + (T2 T1 )
1 n
R c p cv c p ncv
= m(T2 T1 )(cv + ) = m(T2 T1 )(cv + ) = m(T2 T1 )( ) = mc n (T2 T1 )
1 n 1 n 1 n
c p ncv
, where c n = is called the polytropic specific heat.
1 n
Internal energy, enthalpy, and specific heats of solids and liquids
The specific volume is very small, then dh = du + d ( Pv ) = du + vdP du cdT ,

c p c v = c , h = h2 h1 u = u 2 u1 = c(T2 T1 )

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dh = du + vdP , h = u + vP , The constant pressure

processes h = u = c(T2 T1 ) , The constant temperature processes
h = vP .
Refrigeration and freezing of foods

Siebels formula: c p , fresh = 3.35a + 0.84[kJ / kg 0C ], c p , frozen = 1.26a + 0.84[kJ / kg 0C ] ,

where a is the fraction of water content of the food.

Latent heat: hlatent = 334a (kJ / kg )

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 13

Chapter 5: The first law of thermodynamics: Control Volumes

Conservation of mass
Considering a control volume, during a time interval t let the mass mi enter the
control volume, and let the mass me leave the control volume. Further, the
mass within the control volume at the beginning of this time interval is mt and
the mass within the control volume after this interval is mt +t . At the time t the
total mass is mt + mi and time t + t the total mass is mt +t + me .
Then, for the law of conservation of mass, we can write
mt + mi = mt +t + me , (mt +t mt ) + me mi = 0 . The average rate of change
of the mass within the control volume during t is
m t + t m t m e m i
+ = 0 , and the instantaneous rate form becomes
t t t
dm
+ m& e m& i = 0 .
dt cv

In the control volume, the total mass mcv , we obtain mcv = dv and
cv

dm d
= cv dv . The amount of mass crosses the surface A is given
dt cv dt

m& = Vn dA , where is the fluid density, Vn is the velocity normal to the

A

surface A . Then, m& e

= Vn dAe and
Ae
m& =
i
Ai
Vn dAi . Therefore,

d
dt cv
dv + Vn dAe Vn dAi = 0
Ae Ai

V A V A
For steady state one-dimension flow eVe Ae = iVi Ai , or e e = i i , therefore,
ve vi

for steady state one-dimensional flow the continuity equation is given

VA
m& = = AV = cons.
v
The first law as a rate equation
Consider a time interval t during which an amount of heat Q crosses the system
boundary, an amount of work W is done by the system, from the first law we
have Q = E + W Dividing by t and taking the limit, we have
Q E W dE &
= + , and Q& = +W
t t t dt
The first law of thermodynamics for a control volume

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 14

Consider the control volume during the time interval t , the mass mi enters the
control volume through the discrete area Ai , and the mass me leaves the
control volume through the area Ae . The first law as a rate equation is
Q E 2 E1 W
= + .
t t t
At time t the total energy E1 = Et + mi ei and at the time t + t the total energy
E 2 = Et +t + me ee . Therefore E 2 E1 = Et +t Et + me ee mi ei
The work done by mass mi as it enters the control volume is Pi vi mi and the
work done by mass me as it leaves the control volume is Pe v eme . Thus the
total work is W = Wcv + (Pe v eme Pi vi mi ) , where Wcv is the work that
crosses the control surface during t .
Substitute to the first law rate equation
Q E t + t E t m e
= + (ee + Pe ve ) mi (ei + Pi vi ) + Wcv
t t t t t
V 2 V 2
The term e + Pv can be rewritten as e + Pv = u + + gz + Pv = h + + gz .
2 2
Therefore

Q E t + t E t m e V
2
m V 2 Wcv
= + he + e + gz e i hi + i + gz i +
t t t 2 t 2 t

In utilizing the limiting values to express the rate equation of the first law for a control

dE V 2 V 2
volume as Q& cv = cv + m& e he + e + gz e m& i hi + i + gz i + W& cv
dt 2 2
For steady-state, steady-flow process, such as turbines, compressors, nozzles, boilers,

and condensers: The continuity equation m& m&

e i = 0 , The first law

V 2 V 2
Q& cv = m& e he + e + gz e mi hi + i + gz i + W& cv
2 2
For uniform-state, uniform-flow process, such as filled closed tank with gases or
liquids or discharged from closed vessels.

The continuity equation is (m2 m1 )cv + me mi = 0 , the first law

V 2 V 2
Qcv = m2 u 2 + 2 + gz 2 m1 u1 + 1 + gz1
2 2 cv

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 15

V 2 V 2
+ me he + e + gz e mi hi + i + gz i + Wcv
2 2
The throttling process: h2 = h1
T
The Joule-Thomson coefficient is defined: J =
P h

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 16

Chapter 6: The second law of thermodynamics

The second law of thermodynamics
A hot cup of coffee cools by virtue of heat transfer to the surroundings, but heat will
not flow from the cooler surroundings to the hotter cup of coffee.
Gasoline is used as a car drives up to hill, but on coasting down the hill, the fuel level
in the gasoline tank cannot be restored to its original level.
The Kelvin-Planck statement:
It is impossible to construct a heat engine that operates in a cycle and receives a given
amount of heat from a high-temperature body and does an equal amount of work.
The Clausius statement:
It is impossible to construct a device that operates in cycle and produces no effect
other than the transfer of heat from a cooler body to a hotter body.
A cycle violates the Clausius statement that must also violate the Kelvin-Planck
statement
The reversible process
A reversible process for a system is defined as a process that once having taken place
can be reversed and in no so doing leaves no change in either system or
surroundings.
Factors make the processes irreversible.
z Friction
z Unrestrained expansion
z Heat transfer through a finite temperature difference
z Mixing of two different substance
z Hysteresis effect
z i 2 R loss
z Combustion
z Other factors
The reversible cycle
z A reversible cycle is a system go through a number of different reversible
processes and finally returns to its initial state.
Thermal energy reservoir
z A hypothetical body with a relatively large thermal energy capacity that can
supply or absorb finite amounts of heat without undergoing any change in
temperature.
z Heat source
z Heat sink
Heat engines

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 17

Wnet QH QL Q
The thermal efficiency is defined as th = = = 1 L
QH QH QH
Refrigerators
The coefficient of performance COP is defined as
QL QL 1
COP = = =
W QH QL QH 1
QL
Heat pumps
The coefficient of performance COP is defined as
QH QH 1
COP = = =
W QH QL 1 QL
QH
Air conditioners
Energy Efficiency Rating(EER): EER=3.412COP
The Carnot Cycle
z Process 1-2 a reversible isothermal process
z Process 2-3 a reversible adiabatic process
z Process 3-4 a reversible isothermal process
z Process 4-1 a reversible adiabatic process
Q
z th = 1 L
QH
2 V2
z In 1-2 process Q = dU + W , QH = W = PdV = mRTH ln
1 V1
V3
mRTL ln
V Q V4
z Similarly, QL = W = mRTL ln 3 , th = 1 L = 1
V4 QH V
mRTH ln 2
V1
1 1
T V T V
z For ideal gas Q T1 = T2 , T3 = T4 , 3 = 2 , and 4 = 1
T2 V3 T1 V4

V2 V1 T
z = , th = 1 L
V3 V4 TH
z Mean effective pressure Pm : Wnet = Pm V13 = Pm piston displacement ,
Wnet
P m =
V13
The reversed Carnot cycle
QL
z The COP is COP =
QH QL

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 18

V2 V
z QL = W12 = mRTL ln , and QH = mRTH ln 3
V1 V4
V2 V3 TL
z Q = , COP =
V1 V4 TH TL
QH TH
z The heat pump COP = =
QH QL TH TL
Two propositions regarding the efficiency of a reversible cycle
It is impossible to construct an engine that operates between two given reservoirs and
is more efficient than a reversible engine operating between the same two
reservoirs.
All engines that operate on the reversible cycle between two given constant
temperature reservoirs have the same efficiency.
The thermodynamic temperature scale

QH (TH ) QH T
Kelvin scale = , = H
QL (TL ) QL rev TL

Suppose we had a heat engine operating on the reversible cycle that between the ice
point and the steam temperature reservoirs. If the efficiency of such an engine
T
could be measured, it would be found to be 26.8%. th = 1 ice = 0.268 ,
Tsteam
Tice
= 0.732
Tsteam
If we wish to have the magnitude of the degree on the absolute scale correspond to the
magnitude of the degree on the Celsius, then Tsteam Tice = 100
Solving these two equations, we have Tsteam = 373.15K , Tice = 273.15K

The Fahrenheit scale: Tsteam T ice= 180 , Tsteam = 671.67 0 R, Tice = 491.67 0 R

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Chapter 7: Entropy
Inequality of Clausius
Q
z It is a consequence of the second law of thermodynamics T
0

T
z Reversible heat engine cycle: Q = QH QL = W = QH 1 L > 0 ,
TH

T QH QL Q QH QL
QL = QH L
TH
,
TH
=
TL
, T
=
TH TL
= 0 Therefore, for all reversible

Q
heat engine cycles Q 0,
T
=0

z Irreversible cycle heat engine: Wr > Wir ,

T
Q' L > QL , QL Q' L < 0 , Q = Q H Q ' L = Wir 0 , QL = QH 1 ,
T2
QH Q' L Q Q H Q ' L
< 0, = < 0 , Thus for all irreversible heat engine
T2 T1 T T2 T1
Q
cycles Q 0, T
<0

Q
z Similarly for all the reversible refrigeration cycles: Q 0, T
= 0 , and for

Q
all the irreversible cycles: Q < 0, T
<0

Entropy
z By the use of inequality of Clausius in a cycle, it may be shown that the second
law of thermodynamics leads to a property of a system that we call entropy.
z A reversible cycle, goes a reversible process from state 1 to state 2 along path A,
and completes along path B. From inequality of Clausius for reversible cycle we
Q Q 2 Q 1 Q 2 Q 2 Q
have = 0 , and = + = 0 , =
T T 1
T A 2 T B 1
T A 1 T B
z Paths A and B are the arbitrary paths. Thus , for a arbitrary path between state 1
2 Q 2 Q 2 Q
and state 2 has = = =C
1 T 1
T A 1 T B
z Therefore, this quantity is independent of the path and is a function of state only,
Q
and is a property. The property is called entropy and defined as dS = ,
T rev

19
 20

2 Q
and S = S 2 S1 =
1
T rev
z If the path C is a irreversible process,
2 Q 1 Q 2 Q 1 Q Q Q
then + = 0, + < 0 , > ,
1
T A 2 T B 1
T A 2 T C T B T C
Q 2 Q
dS > , S = S 2 S1 > 1
T ir T ir
2 Q Q 2 Q
z Therefore S 2 S1 , or dS , S sys = S 2 S1 = + S gen
1 T T 1 T
Principle of the increase of entropy
Q Q
z For the system dS sys , for the surroundings dS surr , the total net
T T0
Q Q
change of entropy is dS net = dS sys + dS surr , since T0 > T ,
T T0
dS net 0
z The great significance is that the only processes that can take place are those in
which the net change in entropy of the system plus its surroundings increases.
If the process is adiabatic process Q = 0, dS 0
z S = S 2 S1 = 0 reversible process
z S = S 2 S1 > 0 irreversible process
The reversible and adiabatic process is called isentropic process.
s = 0, or , s 2 = s1
Property diagram involving entropy

The T-s diagram: Q = TdS , q = Tds ,for a reversible and isothermal process
2 2

1 1

Q = T S , q = T s
The h-s diagram : The Mollier diagram
Entropy change of pure substances

In the saturation region the entropy may be calculated using the quality s = s f + xs fg

S = ms = m( s 2 s1 )
What is the entropy?
Entropy can be viewed as a measure of molecular disorder, or molecular randomness.
The third law of thermodynamicsThe entropy of a pure crystalline substance at
absolute zero temperature is zero since there is no uncertainty about the state of
the molecules at that instant.
The ds relations
z q = du + w , Q q = Tds , w = Pdv , Tds = du + Pdv

20
 21

z h = u + Pv , dh = du + Pdv + vdP , du = dh Pdv vdP , Tds = dh vdP

du Pdv dh vdP
z ds = + , ds =
T T T T
Entropy change in reversible processes
The Carnot cycle:
2 Q Q 4 Q Q
S12 = = H , S 34 = = L , QH = TH S12 , QL = TL S 34 ,
1
T rev TH 3
T rev TL
Wnet T
Wnet = QH QL = (TH TL )S , th = = 1 L
QH TH
Entropy change of liquids and solids:
du cdT
z Tds = du + Pdv , for the solids and liquids dv 0 , ds = , since
T T

T
c v = c p = c , s = s 2 s1 = c ln 2
T1

The entropy change of ideal gases:

du P P R du dv
From the ds relations ds = + dv , Pv = RT , = , ds = +R ,
T T T v T v
dT dv T v
du = cv dT , ds = cv + R , s = s 2 s1 = cv ln 2 + R ln 2
T v T1 v1
dh vdP dT dP
ds = , Pv = RT , dh = c p dT , ds = c p R ,
T T T P
T P
s = s 2 s1 = c p ln 2 R ln 2
T1 P1
It is convenient to perform these integrals once and tabulate the result. For this
purpose, we choose absolute zero as the reference temperature and define a
T dT 2 dT
function s 0 as s 0 = c p , cp = s 20 s10 ,
o T 1 T
P
s = s 2 s1 = s 20 s10 R ln 2
P1
Isentropic processes of ideal gases
dP dP c p dT
q = Tds = dh vdP = 0 , dh = vdp = RT = c p dT , = ,
P P R T
P 1 T dT
ln 0
= cp , the relative pressure Pr is defined
P R T0 T
P 1 T dT
as ln Pr = ln 0
= cp , for isentropic process s = 0 ,
P R T0 T

21
 22

s 2o s10 P2 sT2 sT1 P P v

0 0
P v
= ln = = ln r 2 , 1 = r1 , and 1 = r1
R P1 R Pr1 P2 Pr 2 s v2 vr 2 s

The second law of thermodynamics for a control volume

The entropy entering the control volume + the increased entropy = the entropy leaving
the control volume + the change of entropy inside the control volume
Q& ds ds
m& i si + cv T
+
dt increase
= m& e s e +
dt cv
ds Q& ds
= m& e s e m& i si + 0
dt increase cv T dt cv

ds Q&
+ m& e s e m& i si
dt cv cv T

Q&
The steady-state steady-flow process : m& s m& s T , if an adiabatic
e e i i
cv

process m& s m& s

e e i i 0 , if m& e = m& i , se si

The uniform-state, uniform-flow process:

&
(m2 s 2 m1 s1 )cv + me se mi si 0 Q dt
t

cv T

Principle of the increase of entropy for a control volume:

ds Q&
+ m& e s e m& i si
dt cv cv T

ds Q&
m& e s e + m& i si
dt surr T0
ds ds ds Q& Q&
= + , since Q& > 0 when T0 > T and Q& < 0
dt net dt cv dt surr cv T T0
ds
when T0 < T , 0
dt net
Efficiency
W
Heat engine : th = net
QH
Wactual
Turbine: turbine =
Wisentropic

Vactual
2

Nozzle: nozzle = 2
2
Visentropic
2

22
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Wisentropic
Compressor: Comp =
Wactual
Reversible steady-flow work
z In the steady-state steady-flow and isentropic process

Tds = dh vdP, dh = vdP, he hi = vdP

e

z The first law for unit mass

Ve2 Vi 2 Ve2 Vi 2
w = (he hi ) g ( z e z i ) , w = vdP g (z e z i )
e

2 i 2
Ve2 Vi 2
z Incompressible fluid: w = v( Pe Pi ) g (z e zi )
2
z Ideal gas
z Isothermal process: Pv = C ,
P 1
( ) v 1
( )
w = RT ln e Ve2 Vi 2 g ( z e z i ) = RT ln i Ve2 Vi 2 g ( z e z i )
Pi 2 ve 2

z Polytropic process: Pv n = C ,

w=
n
n 1
( ) ( )
(Pe ve Pi vi ) 1 Ve2 Vi 2 g ( z e z i ) = nR (Te Ti ) 1 Ve2 Vi 2 g ( z e z i )
2 n 1 2

z Isentropic process: Pv = C ,

w=

1
( ) ( )
(Pe ve Pi vi ) 1 Ve2 Vi 2 g (z e z i ) = R (Te Ti ) 1 Ve2 Vi 2 g (z e z i )
2 1 2

Entropy balance
Qk
z Closed systems: S system = S 2 S1 = + S gen
Tk
Q&
z Control volumes: S cv = (S 2 S1 )cv = k ( m& e s e m& i si ) + S& gen
Tk
Jump 6-11,6-12

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