KMK20003

THERMODYNAMICS FOR CHEMICAL ENGINEERING

CHAPTER 1
INTRODUCTION & BASIC CONCEPT
WEEK 1

1
1.1 Introduction to Thermodynamics
Thermodynamics can be defined as the science
of energy.

Energy can be viewed as the ability to cause

changes.

One of the most fundamental laws of nature is

the conservation of energy principle. It simply
states that during an energy interaction, energy
can change from one form to another but the
total amount of energy remains constant. That
is, energy cannot be created or destroyed.

For example, in Figure 1-1, a rock falling off a

cliff, picks up speed as a result of its potential
energy being converted to kinetic energy.

2
1.1 Introduction to Thermodynamics
The conservation of energy principle also
forms the backbone of the diet industry.

A person who has a greater energy input

(food) than energy output (exercise) will
gain weight (store energy in the form of
fat), and a person who has a smaller
energy input than output will lose weight
(Figure 1–2).

The change in the energy content of a

body or any other system is equal to the
difference between the energy input and
the energy output, and the energy balance
is expressed as
Ein - Eout = ∆E.

3
1.1 Introduction to Thermodynamics
The first law of thermodynamics is simply
an expression of the conservation of energy
principle, and it asserts that energy is a
thermodynamic property.

The second law of thermodynamics asserts

that energy has quality as well as quantity,
and actual processes occur in the direction
of decreasing quality of energy.

For example, a cup of hot coffee left on a

table eventually cools, but a cup of cool
coffee in the same room never gets hot by
itself (Figure 1–3).

The high-temperature energy of the coffee

is degraded (transformed into a less useful
form at a lower temperature) once it is
transferred to the surrounding air. 4
1.1 Introduction to Thermodynamics
It is well-known that a substance consists of a large number of particles called
molecules. The properties of the substance naturally depend on the behaviour of
these particles.

For example, the pressure of a gas in a container is the result of momentum transfer
between the molecules and the walls of the container.

However, one does not need to know the behaviour of the gas particles to determine
the pressure in the container.

The macroscopic approach to the study of thermodynamics that does not require a
knowledge of the behaviour of individual particles. It is also known as classical
thermodynamics. It provides a direct and easy way to the solution of engineering
problems.

The microscopic approach are more elaborate, based on the average behaviour of
large groups of individual particles, and also known as statistical thermodynamics.

5
1.2 Application of Thermodynamics
All activities in nature involve some interaction
between energy and matter; thus, it is hard to
imagine an area that does not relate to
thermodynamics in some manner.

Therefore, developing a good understanding

of basic principles of thermodynamics has
long been an essential part of engineering
education.

Most ordinary household utensils and

appliances are designed, in whole or in part,
by using the principles of thermodynamics.
(Figure 1-4)

Some examples include the electric or gas

range, the heating and air-conditioning
systems, the refrigerator, the humidifier, the
pressure cooker, the water heater, the 6
shower, the iron, and even the computer and
1.2 Application of Thermodynamics
On a larger scale, thermodynamics plays a major part in the design and analysis of
automotive engines, rockets, jet engines, and conventional or nuclear power plants,
solar collectors, and the design of vehicles from ordinary cars to airplanes (Figure
1–5).

7
1.3 System and Control Volume
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. The real or
imaginary surface that separates the system from its surroundings is called the
boundary (Figure 1–6).

The boundary of a system can be fixed or movable. Note that the boundary is the
contact surface shared by both the system and the surroundings

8
1.3 System and Control Volume
Systems may be considered to be closed or open, depending on whether a fixed
mass or a fixed volume in space is chosen for study.

A closed system (also known as a control mass or just system when the context
makes it clear) consists of a fixed amount of mass, and no mass can cross its
boundary. That is, no mass can enter or leave a closed system, as shown in Figure
1–7. But energy, in the form of heat or work, can cross the boundary; and the
volume of a closed system does not have to be fixed.

9
1.3 System and Control Volume
Consider the piston-cylinder device
shown in Figure 1–8.

Let us say that we would like to find out

what happens to the enclosed gas when
it is heated.

Since we are focusing our attention on

the gas, it is our system.

The inner surfaces of the piston and the

cylinder form the boundary, and since no
mass is crossing this boundary, it is a
closed system.

Notice that energy may cross the

boundary, and part of the boundary.

10
1.3 System and Control Volume
An open system, or a control volume, as
it is often called, is a properly selected
region in space.

It usually encloses a device that involves

mass flow such as a compressor,
turbine, or nozzle.

A large number of engineering problems

involve mass flow in and out of a system
and, therefore, are modelled as control
volumes.

A water heater, a car radiator, a turbine,

and a compressor all involve mass flow
and should be analysed as control
volumes (open systems) instead of as
control masses (closed systems). Figure
1–9. 11
1.4 Properties of a System
Any characteristic of a system is called a property.

Some familiar properties are pressure P, temperature T, volume V, mass m,

viscosity, thermal conductivity, modulus of elasticity, thermal expansion
coefficient, electric resistivity, and even velocity and elevation.

Properties are considered to be either intensive or extensive.

Intensive properties are those that are independent of the mass of a system,
such as temperature, pressure, and density.

Extensive properties are those whose values depend on the size—or extent—of
the system.

Total mass, total volume, and total momentum are some examples of extensive
properties.

12
1.4 Properties of a System
An easy way to determine whether a property
is intensive or extensive is to divide the
system into two equal parts with an imaginary
partition, as shown in Fig. 1–10.

Each part will have the same value of

intensive properties as the original system,
but half the value of the extensive properties.

Extensive properties per unit mass are called

specific properties. Some examples of
specific properties are specific volume (v 5
V/m) and specific total energy (e 5 E/m).

13
1.4 Properties of a System
Since some of the thermodynamic relations that are applicable to closed and open
systems are different, it is extremely important that we recognize the type of system
we have before we start analyzing it.

Any characteristic of a system in equilibrium is called a property. The property is

independent of the path used to arrive at the system condition.

Some thermodynamic properties are pressure P, temperature T, volume V, and

mass m.

Properties may be intensive or extensive.

Extensive properties are those that vary directly with size--or extent--of the system.

Some Extensive Properties

a. mass
b. volume
c. total energy
d. mass dependent property

14
1.4 Properties of a System
Intensive properties are those that are independent of size.

Some Intensive Properties

a. temperature
b. pressure
c. age
d. color
e. any mass independent property

15
1.4 Properties of a System
Extensive properties per unit mass are intensive properties. For example, the
specific volume v, defined as

Volume V m 
 3
v   
mass m  kg 
and density , defined as

mass m  kg 
   3
are intensive properties.
volume V  m 

16
1.5 State, Equilibrium and Properties State

Consider a system that is not undergoing any change. The properties can be
measured or calculated throughout the entire system. This gives us a set of
properties that completely describe the condition or state of the system. At a given
state all of the properties are known; changing one property changes the state.

1.5.1 Equilibrium

A system is said to be in thermodynamic equilibrium if it maintains thermal (uniform

temperature), mechanical (uniform pressure), phase (the mass of two phases, e.g.,
ice and liquid water, in equilibrium) and chemical equilibrium.

17
1.5.2. Process

Any change from one state to another is called a process. During a quasi-equilibrium
or quasi-static process the system remains practically in equilibrium at all times. We
study quasi-equilibrium processes because they are easy to analyze (equations of
state apply) and work-producing devices deliver the most work when they operate on
the quasi-equilibrium process.

In most of the processes that we will study, one thermodynamic property is held
constant. Some of these processes are

Process Property held

constant
isobaric pressure System
isothermal temperature Boundary
F
isochoric volume Water
isentropic entropy (see 18
Constant Pressure Process
Chapter 7)
We can understand the concept of a constant pressure process by considering the
above figure. The force exerted by the water on the face of the piston has to equal
the force due to the combined weight of the piston and the bricks. If the combined
weight of the piston and bricks is constant, then F is constant and the pressure is
constant even when the water is heated.

We often show the process on a P-V diagram as shown below.

19
1.5.3 Steady-Flow Process

Consider a fluid flowing through an open system or control volume such as a water
heater. The flow is often defined by the terms steady and uniform. The term steady
implies that there are no changes with time. The term uniform implies no change with
location over a specified region. Engineering flow devices that operate for long
periods of time under the same conditions are classified as steady-flow devices. The
processes for these devices is called the steady-flow process. The fluid properties
can change from point to point with in the control volume, but at any fixed point the
properties remain the same during the entire process.

1.5.4 State Postulate

As noted earlier, the state of a system is described by its properties. But by

experience not all properties must be known before the state is specified. Once a
sufficient number of properties are known, the state is specified and all other
properties are known. The number of properties required to fix the state of a simple,
homogeneous system is given by the state postulate:

The thermodynamic state of a simple compressible system is

completely specified by two independent, intensive properties.

20
1.5.5 Cycle

A process (or a series of connected processes) with identical end states is called a
cycle.

Below is a cycle composed of two processes, A and B.

Along process A, the pressure and volume change from state 1 to state 2. Then to
complete the cycle, the pressure and volume change from state 2 back to the initial
state 1 along process B.

Keep in mind that all other thermodynamic properties must also change so that the
pressure is a function of volume as described by these two processes.

2
P Process
B
1
Process
A

21
1.6 Pressure
Force per unit area is called pressure, and its unit is the pascal, N/m2, in the SI
system and psia, lbf/in2 absolute, in the English system.

N
Force F 1 kPa  103
P  m2
Area A
N
1 MPa  106 2  103 kPa
m

The pressure used in all calculations of state is the

absolute pressure measured relative to absolute zero
pressure. However, pressures are often measured relative
to atmospheric pressure, called gage or vacuum
pressures. In the English system the absolute pressure
and gage pressures are distinguished by their units, psia
(pounds force per square inch absolute) and psig (pounds
force per square inch gage), respectively; however, the SI
system makes no distinction between absolute and gage
pressures. 22
These pressures are related by
Pgage  Pabs  Patm
Pvac  Patm  Pabs
Or these last two results may be written as

Pabs  Patm  Pgage

Where the +Pgage is used when Pabs > Patm and –Pgage is used for a vacuum gage.

The relation among atmospheric, gage, and vacuum pressures is shown below.

23
Some values of 1 atm of pressure are 101.325 kPa, 0.101325 MPa, 14.696 psia, 760
mmHg, and 29.92 inches H2O.

Small to moderate pressure differences are measured by a manometer and a

differential fluid column of height h corresponds to a pressure difference between the
system and the surroundings of the manometer.

This pressure difference is determined from the manometer fluid displaced height as

P   g h ( kPa )

24
1.7 Temperature

Although we are familiar with temperature as a measure of “hotness” or “coldness,” it

is not easy to give an exact definition of it. However, temperature is considered as a
thermodynamic property that is the measure of the energy content of a mass. When
heat energy is transferred to a body, the body's energy content increases and so
does its temperature. In fact it is the difference in temperature that causes energy,
called heat transfer, to flow from a hot body to a cold body. Two bodies are in
thermal equilibrium when they have reached the same temperature. If two bodies are
in thermal equilibrium with a third body, they are also in thermal equilibrium with each
other. This simple fact is known as the zeroth law of thermodynamics.

The temperature scales used in the SI and the English systems today are the Celsius
scale and Fahrenheit scale, respectively. These two scales are based on a specified
number of degrees between the freezing point of water ( 0C or 32F) and the boiling
point of water (100C or 212F) and are related by

9
T F = T  C  32
5 25
Below is a comparison of the temperature scales.
C K F R

99.975 373.125 211.955 671.625 Boiling

point
of water
at 1 atm

0.01 273.16 32.02 491.69 Triple

point of
water

Absolute
0 0 zero
-273.15 -459.67

This figure shows that that according to the International Temperature Scale of 1990
(ITS-90) the reference state for the thermodynamic temperature scale is the triple
point of water, 0.01 C. The ice point is 0C, but the steam point is 99.975C at 1
atm and not 100C as was previously established. The magnitude of the kelvin, K, is
1/273.16 of the thermodynamic temperature of the triple point of water.
26
The magnitudes of each division of 1 K and 1C are identical, and so are the
magnitudes of each division of 1 R and 1F. That is,
 
T K = (T2 C + 273.15) - (T1 C + 273.15)
 
= T2 C - T1 C = T  C
T R  T  F

27
1.8 Energy
Consider the system shown below moving with a velocity, at an elevation Z
relative to the reference plane.

CM 
General V
System

Z 
V

Reference Plane, Z=0

The total energy E of a system is the sum of all forms of energy that can exist
within the system such as thermal, mechanical, kinetic, potential, electric,
magnetic, chemical, and nuclear.

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 (see Section 2-1 of text for 28
more detail).
1.8 Energy
The kinetic energy KE exists as a result of the system's motion relative to an external
 When the system moves with velocity the kinetic energy is
reference frame.
expressed asV
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,

29
 or, on a unit mass basis,

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 )

30
1.8 Energy Transport
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 energy
expended to lift a weight 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:

1.Both 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
31
a process as well as the end states.
Since heat and work are path dependent functions, they have inexact differentials
designated by the symbol . The differentials of heat and work are expressed as Q
and W. The integral of the differentials of heat and work over the process path gives
the amount of heat or work transfer that occurred at the system boundary during a
process.
2


1, along path
 Q  Q12 (not Q)


1, along path
 W  W12 (not W )

That is, the total heat transfer or work is obtained by following the process path and
adding the differential amounts of heat (Q) or work (W) along the way. The
integrals of Q and W are not Q2 – Q1 and W2 – W1, respectively, which are
meaningless since both heat and work are not properties and systems do not
possess heat or work at a state.

The following figure illustrates that properties (P, T, v, u, etc.) are point functions, that
is, they depend only on the states. However, heat and work are path functions, that
is, their magnitudes depend on the path followed.
32
 700 kPa

100 kPa

0.01 m3 0.03 m3

A sign convention is required for heat

and work energy transfers, and the
classical thermodynamic sign
convention is selected for these
notes. According to the classical
sign convention, heat transfer to a System
Boundary
system and work done by a system
are positive; heat transfer from a
system and work a system are
negative. The system shown below
has heat supplied to it and work
done by it. 33
1.8.1 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   Qout

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.

Q
q
m
34
1.8.1 Energy Transport by Heat

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.

35
1.8.2 Energy Transfer by Work

1.8.2a 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

36
1.8.2b 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
37
1.8.2b Mechanical Forms of Work

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.

1.8.2c 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.

We will call these work forms “other” work, that is, work not associated with a moving
boundary. In thermodynamics electrical energy is normally considered to be work
energy rather than heat energy.

38
1.8 First Law of Thermodynamics
The first law of thermodynamics is an expression of the conservation of energy principle.

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 is the velocity of the center of mass.


V

System CM

V
Energyin
Energyout
z

Reference Plane, z = 0

39
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

40
  
V   mV 2
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
1.9.1 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. 41
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 increase;
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

42
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

43
  Ein   Eout   Esystem (kJ )
 e in   eout   esystem (kJ / kg )
1.9.2

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

44
Example 1-1

A system receives 5 kJ of heat transfer and experiences a decrease in energy in the

amount of 5 kJ. Determine the amount of work done by the system.

E= -5 kJ
Qin =5 kJ Wout=?

System
Boundary

We apply the first law as

Ein  Eout  Esystem
Ein  Qin  5 kJ
Eout  Wout
Esystem  5 kJ
Eout  Ein  Esystem
Wout  5   5  kJ
Wout  10 kJ
The work done by the system equals the energy input by heat plus the 45
decrease in the energy of the working fluid.
Example 1-2

A steam power plant operates on a thermodynamic cycle in which water circulates

through a boiler, turbine, condenser, pump, and back to the boiler. For each kilogram
of steam (water) flowing through the cycle, the cycle receives 2000 kJ of heat in the
boiler, rejects 1500 kJ of heat to the environment in the condenser, and receives 5 kJ
of work in the cycle pump. Determine the work done by the steam in the turbine, in
kJ/kg.

46
Qnet  Wnet  Ecycle
Qnet  Wnet
Qin  Qout  Wout  Win
Wout  Qin  Qout  Win
W Q
Let w  and q 
m m
wout  qin  qout  win
kJ
wout   2000  1500  5 
kg
kJ
wout  505
kg

47
Example 1-3

Air flows into an open system and carries energy at the rate of 300 kW. As the air
flows through the system it receives 600 kW of work and loses 100 kW of energy by
heat transfer to the surroundings. If the system experiences no energy change as the
air flows through it, how much energy does the air carry as it leaves the system, in
kW?

System sketch:
Q out

Open
E mass , in System
E mass , out

W in
Conservation of Energy:

E in  E out  E system

E mass ,in  W in  E mass , out  Q out  E system  0
E mass ,out  E mass , in  W in  Q out
E mass ,out  300  600  100  kW  800 kW 48