Chapter 3

Laws of Thermodynamics
After completing this chapter, you have to understand;
1. Laws of thermodynamics (zeroth, First and Second)
2. Forms of Energy
3. Energy conversion mechanisms
4. Energy analysis for closed, steady flow system
5. Entropy
6. Dependence of entropy on temperature and pressure
7. Carnot principles and cycles

2
Energy
 The total energy of the system is normally thought of as the sum of the internal
energy, kinetic energy, and potential energy.
 The internal energy U is that energy associated with the molecular structure of a
system and the degree of the molecular activity. 
 The kinetic energy KE exists as a result of the system's motion V relative to an
external reference frame. When the system moves with velocity the kinetic
energy is expressed as
2
V
KE m ( kJ )
2
The energy that a system possesses as a result of its elevation in a gravitational
field relative to the external reference frame is called potential energy PE and is
expressed as
PE mgZ ( kJ )
where g is the gravitational acceleration and z is the elevation of the center of gravity
of a system relative to the reference frame. The total energy of the system is
expressed as
E U  KE  PE ( kJ )

or, on a unit mass basis,

3
 E U KE PE kJ
e    ( )
m m m m kg
2
V
u   gZ
2
where e = E/m is the specific stored energy, and u = U/m is the specific internal
energy. The change in stored energy of a system is given by
E U  KE  PE ( kJ )
Most closed systems remain stationary during a process and, thus, experience
no change in their kinetic and potential energies. The change in the stored energy is
identical to the change in internal energy for stationary systems.

If KE = PE = 0,

E U ( kJ )

4
Energy Transport by Heat and Work and the Classical Sign Convention

Energy may cross the boundary of a closed system only by heat or work.

Energy transfer across a system boundary due solely to the temperature difference
between a system and its surroundings is called heat.

Energy transferred across a system boundary that can be thought of as the pressure
or force applied on or by the system is called work.

Heat and work are energy transport mechanisms between a system and its
surroundings. The similarities between heat and work are as follows:
[Link] are recognized at the boundaries of a system as they cross the boundaries.
They are both boundary phenomena.
2. Systems possess energy, but not heat or work.
3. Both are associated with a process, not a state. Unlike properties, heat or work
has no meaning at a state.
4. Both are path functions (i.e., their magnitudes depends on the path followed
during a process.
5
 System
Boundary
Energy Transport by Heat

Recall that heat is energy in transition across the system boundary solely due to the
temperature difference between the system and its surroundings. The net heat
transferred to a system is defined as
Qnet  Qin  Q out
Here, Qin and Qout are the magnitudes of the heat transfer values. In most
thermodynamics texts, the quantity Q is meant to be the net heat transferred to the
system, Qnet. Since heat transfer is process dependent, the differential of heat
transfer Q is called inexact. We often think about the heat transfer per unit mass of
the system, q. 6
 Q
q
m
Heat transfer has the units of energy measured in joules (we will use kilojoules, kJ) or
the units of energy per unit mass, kJ/kg.

Since heat transfer is energy in transition across the system boundary due to a
temperature difference, there are three modes of heat transfer at the boundary that
depend on the temperature difference between the boundary surface and the
surroundings. These are conduction, convection, and radiation. However, when
solving problems in thermodynamics involving heat transfer to a system, the heat
transfer is usually given or is calculated by applying the first law, or the conservation
of energy, to the system.

An adiabatic process is one in which the system is perfectly insulated and the heat
transfer is zero.

7
Energy Transfer by Work

1. Electrical Work

The rate of electrical work done by electrons crossing a system boundary is called
electrical power and is given by the product of the voltage drop in volts and the
current in amps.

W e V I (W)

The amount of electrical work done in a time period is found by integrating the rate of
electrical work over the time period.

2
We V I dt (kJ)
1

8
2. Mechanical Forms of Work

Work is energy expended by a force acting through a distance. Thermodynamic work

is defined as energy in transition across the system boundary and is done by a
system if the sole effect external to the boundaries could have been the raising of a
weight.

Mathematically, the differential of work is expressed as

 
 W  F d s  F ds cos
here  is the angle between the force vector and the displacement vector.
As with the heat transfer, the Greek symbol  means that work is a path-dependent
function and has an inexact differential. If the angle between the force and the
displacement is zero, the work done between two states is
2 2
W12 W  Fds
1 1
9
Work has the units of energy and is defined as force times displacement or newton
times meter or joule (we will use kilojoules). Work per unit mass of a system is
measured in kJ/kg.

Common Types of Mechanical Work Energy (See text for discussion of these
topics)

•Shaft Work
•Spring Work
•Work done of Elastic Solid Bars
•Work Associated with the Stretching of a Liquid Film
•Work Done to Raise or to Accelerate a Body

Net Work Done By A System

The net work done by a system may be in two forms other work and boundary
work. First, work may cross a system boundary in the form of a rotating shaft
work, electrical work or other the work forms listed above.
Boundary work is related to compression and expansion of system boundary.

10
The First Law of Thermodynamics

The first law of thermodynamics is known as the conservation of energy principle. It states
that energy can be neither created nor destroyed; it can only change forms. Joule’s
experiments lead to the conclusion: For all adiabatic processes between two specified states of
a closed system, the net work done is the same regardless of the nature of the closed system
and the details of the process. A major consequence of the first law is the existence and
definition of the property total energy E introduced earlier.

Energy can cross the boundaries of a closed system in the form of heat or work. Energy may
cross a system boundary (control surface) of an open system by heat, work and mass
transfer.

A system moving relative to a reference planeis shown below where z is the elevation of the
center of mass above the reference plane and V is the velocity of the center of mass.

System CM

V
Energyi
Energyout
n
z

Reference Plane, z = 0

11
For the system shown above, the conservation of energy principle or the first law
of thermodynamics is expressed as
 Total energy   Total energy   The change in total 
      
 entering the system   leaving the system   energy of the system 

or
Ein  Eout E system
Normally the stored energy, or total energy, of a system is expressed as the
sum of three separate energies. The total energy of the system, Esystem, is given as
E = Internal energy + Kinetic energy + Potential energy
E = U + KE + PE
Recall that U is the sum of the energy contained within the molecules of the system
other than the kinetic and potential energies of the system as a whole and is called
the internal energy. The internal energy U is dependent on the state of the system
and the mass of the system.

For a system moving relative to a reference plane, the kinetic energy KE and the
potential energy PE are given by

12
  2
V  mV
KE   mV dV 
V 0 2
z
PE  mg dz mgz
z 0

The change in stored energy for the system is

E U  KE  PE

Now the conservation of energy principle, or the first law of thermodynamics for
closed systems, is written as
Ein  Eout U  KE  PE
If the system does not move with a velocity and has no change in elevation, it is
called a stationary system, and the conservation of energy equation reduces to

Ein  Eout U

Mechanisms of Energy Transfer, Ein and Eout

The mechanisms of energy transfer at a system boundary are: Heat, Work, mass
flow. Only heat and work energy transfers occur at the boundary of a closed (fixed
mass) system. Open systems or control volumes have energy transfer across
the control surfaces by mass flow as well as heat and work. 13
1. Heat Transfer, Q: Heat is energy transfer caused by a temperature difference
between the system and its surroundings. When added to a system heat transfer
causes the energy of a system to increase and heat transfer from a system
causes the energy to decrease. Q is zero for adiabatic systems.

2. Work, W: Work is energy transfer at a system boundary could have caused a

weight to be raised. When added to a system, the energy of the system
increases; and when done by a system, the energy of the system decreases. W
is zero for systems having no work interactions at its boundaries.

3. Mass flow, m: As mass flows into a system, the energy of the system increases
by the amount of energy carried with the mass into the system. Mass leaving the
system carries energy with it, and the energy of the system decreases. Since no
mass transfer occurs at the boundary of a closed system, energy transfer by mass
is zero for closed systems.

The energy balance for a general system is

Ein  Eout Qin  Qout   Win  Wout 

  Emass , in  Emass , out  Esystem

14
Expressed more compactly, the energy balance is
E  E  Esystem (kJ )
 in   out   
Net energy transfer Change in internal, kinetic,
by heat, work, and mass potential, etc., energies

or on a rate form, as

E in  E out  E system ( kW )

     
Rate of net energy transfer Rate change in internal, kinetic,
by heat, work, and mass potential, etc., energies

For constant rates, the total quantities during the time interval t are related to the
quantities per unit time as
Q Q t , W W t , and E E t (kJ )
The energy balance may be expressed on a per unit mass basis as

e in  eout esystem (kJ / kg )

and in the differential forms as

15
  Ein   Eout  Esystem (kJ )
 e in   eout  esystem (kJ / kg )
First Law for a Cycle

A thermodynamic cycle is composed of processes that cause the working fluid to

undergo a series of state changes through a process or a series of processes. These
processes occur such that the final and initial states are identical and the change in
internal energy of the working fluid is zero for whole numbers of cycles. Since
thermodynamic cycles can be viewed as having heat and work (but not mass)
crossing the cycle system boundary, the first law for a closed system operating in a
thermodynamic cycle becomes
Qnet  Wnet Ecycle
Qnet Wnet

16
Some Typical Processes for Energy Analysis of Closed Systems

Constant volume process

If the volume is held constant, dV = 0, and the boundary work equation becomes
P 1

P-V diagram for V = constant

If the working fluid is an ideal gas, what will happen to the temperature of the gas
during this constant volume process?

17
 Constant pressure process
P
2 1

P-V DIAGRAM for P = CONSTANT

If the pressure is held constant, the boundary work equation becomes

For the constant pressure process shown above, is the boundary work positive or
negative and why?

Chapter 4 18
Constant temperature process, ideal gas

If the temperature of an ideal gas system is held constant, then the equation of
state provides the pressure-volume relation
mRT
P
V
Then, the boundary work is

Note: The above equation is the result of applying the ideal gas assumption for
the equation of state. For real gases undergoing an isothermal (constant
temperature) process, the integral in the boundary work equation would be done
numerically.

Chapter 4 19
The polytropic process

The polytropic process is one in which the pressure-volume relation is given

as

n
PV constant
The exponent n may have any value from minus infinity to plus infinity
depending on the process. Some of the more common values are given below.
Process
Exponent n
Constant pressure 0
Constant volume 
Isothermal & ideal gas 1
Adiabatic & ideal gas k=
CP/CV

Here, k is the ratio of the specific heat at constant pressure CP to specific

heat at constant volume CV. The specific heats will be discussed later.

Chapter 4 20
The boundary work done during the polytropic process is found by substituting
the pressure-volume relation into the boundary work equation. The result is

Note: for the polytropic process the constant, Const = P1V1 = P2V2

Notice that the result we obtained for an ideal gas undergoing a

polytropic process when n = 1 is identical to that for an ideal gas
undergoing the isothermal process.

Chapter 4 21
Specific Heats and Changes in Internal Energy and Enthalpy for Ideal
Gases

Before the first law of thermodynamics can be applied to systems, ways to

calculate the change in internal energy of the substance enclosed by the
system boundary must be determined. For real substances like water, the
property tables are used to find the internal energy change. For ideal gases
the internal energy is found by knowing the specific heats. Physics defines
the amount of energy needed to raise the temperature of a unit of mass of a
substance one degree as the specific heat at constant volume CV for a
constant-volume process, and the specific heat at constant pressure CP for a
constant-pressure process. Recall that enthalpy h is the sum of the internal
energy u and the pressure-volume product Pv.

h u  Pv

Chapter 4 22
 In thermodynamics, the specific heats are defined as

Simple Substance

The thermodynamic state of a simple, homogeneous substance is specified by giving

any two independent, intensive properties. Let's consider the internal energy to be a
function of T and v and the enthalpy to be a function of T and P as follows:

u u (T , v) and h h(T , P)
The total differential of u is

Chapter 4 23
The total differential of h is

Using thermodynamic relation theory, we could evaluate the remaining partial

derivatives of u and h in terms of functions of P,v, and T. These functions depend
upon the equation of state for the substance. Given the specific heat data and the
equation of state for the substance, we can develop the property tables such as the
steam tables.
Ideal Gases

For ideal gases, we use the thermodynamic function theory of Chapter 12 and the
equation of state (Pv = RT) to show that u, h, CV, and CP are functions of
temperature alone.

For example when total differential for u = u(T,v) is written as above, the function
theory of Chapter 12 shows that
Chapter 4 24
  u 
du Cv dT    dv
 v  T
  P  
du Cv dT   T    P  dv
  T  v 
Let’s evaluate the following partial derivative for an ideal gas.

For ideal gases

Chapter 4 25
This result helps to show that the internal energy of an ideal gas does not depend
upon specific volume. To completely show that internal energy of an ideal gas is
independent of specific volume, we need to show that the specific heats of ideal
gases are functions of temperature only. We will do this later in Chapter 12. A
similar result that applies to the enthalpy function for ideal gases can be reviewed in
Chapter 12.

Then for ideal gases,

The ideal gas specific heats are written in terms of ordinary differentials as

Chapter 4 26
where CV,ave and CP,ave are average or constant values of the specific heats over the
temperature range. We will drop the ave subscript shortly.
2a
P
2b
1 2c
T2
T1

P-V diagram for several processes for

an ideal gas.
In the above figure an ideal gas undergoes three different process between the same
two temperatures.

Process 1-2a: Constant volume

Process 1-2b: P = a + bV, a linear relationship
Process 1-2c: Constant pressure

These ideal gas processes have the same change

Chapter 4 in internal energy and enthalpy27
because the processes occur between the same temperature limits.
To find u and h we often use average, or constant, values of the specific heats.
Some ways to determine these values are as follows:

[Link] best average value (the one that gives the exact results)

See Table A-2(c) for variable specific data.

[Link] average values are

C (T )  CV (T1 ) CP (T2 )  CP (T1 )
Cv ,ave  V 2 CP ,ave  and
2 2
Cv ,ave CV (Tave ) CP ,ave CP (Tave )
where
T2  T1
Tave 
2
Chapter 4 28
[Link] adequate (and most often used) values are the ones evaluated at 300 K
and are given in Table A-2(a).
Cv ,ave CV (300 K ) and CP ,ave CP (300 K )

Let's take a second look at the definition of u and h for ideal gases. Just consider
the enthalpy for now.

Let's perform the integral relative to a reference state where

h = href at T = Tref.

At any temperature, we can calculate the enthalpy relative to the reference state as

Chapter 4 29
A similar result is found for the change in internal energy.
T
u uref   Cv (T )dT 
Tref

These last two relations form the basis of the air tables (Table A-17 on a mass basis)
and the other ideal gas tables (Tables A-18 through A-25 on a mole basis). When
you review Table A-17, you will find h and u as functions of T in K. Since the
parameters Pr, vr, and so, also found in Table A=17, apply to air only in a particular
process, call isentropic, you should ignore these parameters until we study Chapter 7.
The reference state for these tables is defined as
uref 0 at Tref 0 K
href 0 at Tref 0 K
A partial listing of data similar to that found in Table A.17 is shown in the following
figure.
Chapter 4 30
Relation between CP and CV for Ideal Gases

Using the definition of enthalpy (h = u + Pv) and writing the differential of enthalpy,
the relationship between the specific heats for ideal gases is
h u  Pv
dh du  d ( RT )
CP dT CV dT  RdT
CP CV  R
where R is the particular gas constant. The specific heat ratio k (fluids texts often use
 instead of k) is defined as
CP
k
CV
Extra Problem

Show that
kR R
CP  and CV 
k1 k1
Chapter 4 31
Internal Energy and Enthalpy Changes of Solids and Liquids

We treat solids and liquids as incompressible substances. That is, we assume that
the density or specific volume of the substance is essentially constant during a
process. We can show that the specific heats of incompressible substances (see
Chapter 12) are identical.

The specific heats of incompressible substances depend only on temperature;

therefore, we write the differential change in internal energy as
du CV dT CdT

Chapter 4 32
and assuming constant specific heats, the change in internal energy is
u CT C (T2  T1 )
Recall that enthalpy is defined as
h u  Pv
The differential of enthalpy is
dh du  Pdv  vdP
For incompressible substances, the differential enthalpy becomes
dv 0
dh du  Pdv 0  vdP
dh du  vdP
Integrating, assuming constant specific heats
h u  vP CT  vP
For solids the specific volume is approximately zero; therefore,
hsolid usolid  v 0 P
hsolid Chapter
usolid 4CT 33
For liquids, two special cases are encountered:

[Link]-pressure processes, as in heaters (P = 0)

hliquid uliquid CT
[Link]-temperature processes, as in pumps (T = 0)
hliquid uliquid  vP C 0T  vP
hliquid vP

34
Conservation of Mass for General Control Volume

The conservation of mass principle for the open system or control volume is
expressed as

or

 m   m
in out m system ( kg / s)
Steady-State, Steady-Flow Processes

Most energy conversion devices operate steadily over long periods of time. The rates
of heat transfer and work crossing the control surface are constant with time. The
states of the mass streams crossing the control surface or boundary are constant with
time. Under these conditions the mass and energy content of the control volume are
constant with time.
35
 dmCV
m CV 0
dt
Steady-state, Steady-Flow Conservation of Mass:

Since the mass of the control volume is constant with time during the steady-state,
steady-flow process, the conservation of mass principle becomes

or

 m in  m out ( kg / s)
Special Case: Steady Flow of an Incompressible Fluid

The mass flow rate is related to volume flow rate and fluid density by

m  V
For one entrance, one exit steady flow control volume, the mass flow rates are
related by

36
Flow work and the energy of a flowing fluid

Energy flows into and from the control volume with the mass. The energy required to
push the mass into or out of the control volume is known as the flow work or flow
energy.

The fluid up steam of the control surface acts as a piston to push a unit of mass into
or out of the control volume. Consider the unit of mass entering the control volume
shown below.

As the fluid upstream pushes mass across the control surface, work done on that unit
of mass is A
W flow F L F L PV Pmv
A
W flow
w flow  Pv
m 37
The term Pv is called the flow work done on the unit of mass as it crosses the control
surface.

The total energy of flowing fluid

The total energy carried by a unit of mass as it crosses the control surface is the sum
of the internal energy, flow work, potential energy, and kinetic energy.
2
V
 u  Pv   gz
2
2
V
h   gz
2
Here we have used the definition of enthalpy, h = u + Pv.

Energy transport by mass

Amount of energy transport across a control surface:

2
 V 
Emass m m  h   gz  (kJ)
 2 

38
Rate of energy transport across a control surface:
2
 V 
E mass m m  h   gz  (kW )
 2 
Conservation of Energy for General Control Volume

The conservation of energy principle for the control volume or open system has the
same word definition as the first law for the closed system. Expressing the energy
transfers on a rate basis, the control volume first law is

E in  E out  E system ( kW )

or      
Rate of net energy transfer Rate change in internal, kinetic,
by heat, work, and mass potential, etc., energies

Considering that energy flows into and from the control volume with the mass, energy
enters because net heat is transferred to the control volume, and energy leaves
because the control volume does net work on its surroundings, the open system, or
control volume, the first law becomes
39
where  is the energy per unit mass flowing into or from the control volume. The
energy per unit mass, , flowing across the control surface that defines the control
volume is composed of four terms: the internal energy, the kinetic energy, the
potential energy, and the flow work.

The total energy carried by a unit of mass as it crosses the control surface is
2
V
 u  Pv   gz
2
2
V
h   gz
2

Where the time rate change of the energy of the control volume has been written
as E CV 40
Steady-State, Steady-Flow Processes

Most energy conversion devices operate steadily over long periods of time. The rates
of heat transfer and work crossing the control surface are constant with time. The
states of the mass streams crossing the control surface or boundary are constant with
time. Under these conditions the mass and energy content of the control volume are
constant with time.
dmCV
m CV 0
dt
dECV
E CV 0
dt
Steady-state, Steady-Flow Conservation of Mass:

 m in  m out ( kg / s)
Steady-state, steady-flow conservation of energy

Since the energy of the control volume is constant with time during the steady-state,
steady-flow process, the conservation of energy principle becomes

41
or
E in  E out  0 E system ( kW )
     
Rate of net energy transfer Rate change in internal, kinetic,
by heat, work, and mass potential, etc., energies

or

Considering that energy flows into and from the control volume with the mass, energy
enters because heat is transferred to the control volume, and energy leaves because
the control volume does work on its surroundings, the steady-state, steady-flow first
law becomes

42
Often this result is written as

Q net  Q in   Q
out
where
W net  W out   W
in

Steady-state, steady-flow for one entrance and one exit

A number of thermodynamic devices such as pumps, fans, compressors, turbines,

nozzles, diffusers, and heaters operate with one entrance and one exit. The steady-
state, steady-flow conservation of mass and first law of thermodynamics for these
systems reduce to

43
Some Steady-Flow Engineering Devices

Below are some engineering devices that operate essentially as steady-state, steady-
flow control volumes.

44
Nozzles and Diffusers
  
V1 V2  V1

  
V1 V2  V1

For flow through nozzles, the heat transfer, work, and potential energy are normally
neglected, and nozzles have one entrance and one exit. The conservation of energy
becomes


Solving for V2
 2
V2  2(h1  h2 )  V1
45
Turbines

If we neglect the changes in kinetic and

potential energies as fluid flows through an
adiabatic turbine having one entrance and
one exit, the conservation of mass and the
steady-state, steady-flow first law becomes

46
 Compressors and fans

Compressors and fans are essentially the same devices. However, compressors
operate over larger pressure ratios (P2/P1) than fans. If we neglect the changes in
kinetic and potential energies as fluid flows through an adiabatic compressor having
one entrance and one exit, the steady-state, steady-flow first law or the conservation
of energy equation becomes

47
Throttling devices

Consider fluid flowing through a one-entrance, one-exit porous plug. The fluid
experiences a pressure drop as it flows through the plug. No net work is done by the
fluid. Assume the process is adiabatic and that the kinetic and potential energies are
neglected; then the conservation of mass and energy equations become

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This process is called a throttling process. What happens when an ideal gas is
throttled?

When throttling an ideal gas, the temperature does not change. We will see later in
Chapter 11 that the throttling process is an important process in the refrigeration
cycle.

A throttling device may be used to determine the enthalpy of saturated steam. The
steam is throttled from the pressure in the pipe to ambient pressure in the
calorimeter. The pressure drop is sufficient to superheat the steam in the calorimeter.
Thus, the temperature and pressure in the calorimeter will specify the enthalpy of the
steam in the pipe.

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Mixing chambers

The mixing of two fluids occurs frequently in engineering applications. The section
where the mixing process takes place is called a mixing chamber. The ordinary
shower is an example of a mixing chamber. The T-elbow shown in the figure below is
the mixing chamber and may be a simple as ½ inch copper tee.

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Heat exchangers

Heat exchangers are normally well-insulated devices that allow energy exchange
between hot and cold fluids without mixing the fluids. The pumps, fans, and blowers
causing the fluids to flow across the control surface are normally located outside the
control surface.

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Liquid pumps

The work required when pumping an incompressible liquid in an adiabatic steady-

state, steady-flow process is given by

The enthalpy difference can be written as

h2  h1 (u2  u1 )  ( Pv ) 2  ( Pv )1
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