Introduction

The Scope of Thermodynamics

Thermodynamics Variables
Work, Energy, and Heat

Historical Review of Energy Development

Energy: combination of two Greek word, means Capacity & Work

Life, including any event in the physical world, is built on

transformation of energy.

First man used his won physical energy for hunting and building shelters

3000 B.C.: Use of men and animal physical energy

100 B.C.: Invention of water wheel

900 A.D.: harnessed wind energy for sailing and windmills

1711: Development of first steam engine

1831: Practical application of Electric Generator and Electric Motors

1905: Enistein theory

1945: Exploring of atomic bomb

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Present Forms of Energy

Kinetic Energy ~ Motion of an entity that has a mass

Potential Energy ~ Relative location of an entity with mass in a force field

(e.g. in gravitational field)

Chemical Energy ~ Interactions between atomic particles (e.g. released in

an exothermic reaction)

Fuel cells

Nuclear fusion

Photo cells

Utilization of energy from wind, sun, coal, etc.

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The Concept of Caloric

Introduced around 1750s

Temperature of a body changed by contact with another body

Caloric: a substance with neither volume nor mass that could flow
between bodies with different temperature:

A body with high temperature is thought to possess a high caloric value

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Energy Conversion
Potential and kinetics energies are mutually convertible.

1.

Example: Pendulum oscillation

Electrical and thermal energies

2.

Example: Passing electrical current through a resistor

Chemical and thermal energies

3.

Example: Exothermic chemical reaction

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Why Study
Thermodynamics?
Thermodynamics is the science that deals with the transformation of

energy of all kinds from one form to another.

Since any event in the world we live in is accompanied by energy

transformation, thermodynamics is at the core of all science.

In order to apply science for the well being of society, all engineers need to

be acquainted with thermodynamics.

Software packages are nowadays available for calculation of

thermodynamic properties, yet their successful use requires the engineer

to comprehend the science of thermodynamics first.

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Examples of
Thermodynamics
in Chemical Engineering
The chemical engineer designing or simulating a chemical process

needs to evaluate thermodynamic properties of the fluids involved.

Reactor design requires energy balance considerations that involve
enthalpy calculations. Free energy also needs to be evaluated for
equilibrium conversion calculations.
Simulating compressible flow requires enthalpy and entropy

calculations.

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How to Study
Thermodynamics

Thermodynamics can be approached on a microscopic or macroscopic level.

The microscopic approach deals with the motion of molecules, which

involves statistics due to the presence of random activity.

In the macroscopic approach, matter is treated as a continuum. The properties

of matter are attributed to macroscopic variables, such as pressure and

temperature. These variables are results of molecular behavior (microscopic
phenomena).
For example:
Molecules confined in a container hit the walls (microscopic occurrence).
The result of this momentum exchange is referred to as pressure exerted by

the gas (macroscopic observation).

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Engineering Approach to
Thermodynamics
For practical purposes, engineers typically use the macroscopic approach.
This approach to thermodynamics utilizes consistent experiences that have

not been observed otherwise.

General restrictions that are observed to occur within all energy

transformations are called laws.

For example:
First Law of Thermodynamics (Conservation of Energy)

Although energy assumes many forms, the total quantity of energy

remains constant, and when energy disappears in one form it appears
in other forms.
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Thermodynamics has a
language of its own
Thermodynamics starts with only four laws (1st and 2nd being the
most fundamental). All else results from definition or deduction.
In order to apply the thermodynamic method, it is crucial to develop

the ability to proceed logically from one deduction to the next,

making use of precisely defined terms.
Thermodynamics may be treated as complex language.

- First, rigorous meanings are attached to terms (words).

- Then, through logical manipulation, mathematical equations
(sentences) are formulated to reach the desired results.
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Pipes carry all the

materials being processed
in a chemical plant
between the individual
processing
units,
for
example between the
distillation columns and
heat exchangers shown in
the picture.
In most chemical plants
there are miles and miles
of pipes, as you will find
out.

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Basic Concepts
When applying thermodynamics to a real problem, it is necessary to
identify the system.
The system is the part of the universe taken aside for study.

Quantity of matter of fixed mass and identity upon which

attention is focused for study
Surroundings are the rest of the universe (all excluding the system)
The systems thermodynamic state is defined by macroscopic

properties that can be measured (such as pressure).

The macroscopic properties are described in terms of fundamental

scientific dimensions: Length, time, mass, temperature etc.

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Closed and Open Systems

Moving
boundary

(a) Closed Systems:

controlled (fixed) mass.

GAS
GAS
2 kg
1 m3

2 kg
3 m3

Fixed
boundary

Closed
System

mass

NO

(m= constant)

energy YES

(b) Open system: controlled (fixed) volume

Control surface
Hot Water
Out

Water
Heater
(control
volume)

Note:
Volume
is fixed

Cold Water
IN

Thermodynamic State and Equilibrium

Thermodynamic state of a system the condition of the
system as characterized by the values of its properties.
Stable equilibrium state a state in which the system is not
capable of spontaneous change to another state without a
finite change in the surrounding. There are no driving forces
to carry out a change.
There are many different types of equilibria that can be attained:
-

Thermal: the temperature is the same throughout the system.

Mechanical: the pressure is the same.

Phase: no driving force for the total mass in each phase to change.

Chemical: no driving force for chemical composition to change.

We show a state as a point on a phase diagram as long as the

continuum theory applies.

Fundamental Quantities
With our senses, we experience fundamental concepts such as time,
distance, mass and temperature.
These concepts are known through experience, yet in order to give

them quantitative meaning, it is necessary to give them standard units

of measurement.

Definitions of such units have been arbitrary initially. Over time, they

have become standardized.

For example, the fundamental unit of mass is the kilogram, defined in

terms of an (initially arbitrary) platinum/iridium lump.

Internationally accepted units are codified as the International System

of Units (SI). s, m, kg, K, mol

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Measures of Amounts or Size

Common measures of amounts or size:

1. Mass, m 2. Number of moles, n

3. Total volume, Vt [m3]

Relationships between the measures of the amounts or size:

m
n=
M

or

m = Mn

Where M is the molecular weight

Specific or molar volume:

t
V
Specific volume: V =
m
t
V
Molar volume: V =
n

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or

or

Engineering
Thermodynamics

V t = mV
V t = nV
1-17

Intensive and Extensive

Properties
Intensive thermodynamic variables: are those variables which are

independent of the size or amount of the substance (eg., , , T and P)

Extensive thermodynamic variables: are those variables which depend

on the size or amount of the substance (eg., Vt , m and n)
Note: Intensive variables are functions of T , P and composition

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Fundamental Quantities
Force:

Based on Newtons second law of motion:

Unit of force: According to SI system

F ma

kg m s-2 = [N]

Be aware of the engineering for force (lbf): see the textbook

1 lbf = 4.4482216 N
See Example 1.1 (page 4)
Weight properly refers to the force of gravity on a body

Temperature

A measure of degree of hotness by the length of fluid column

SI unit for temperature oC or K: T (K) = T (oC) + 273.15
See the text (p. 5) for explanation of temperature scale

T (oF) = 1.8 T (oC) + 32

T (R) = 1.8 T (oF) + 459.67

Other units: T (R) = 1.8 T (K);

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Temperature and Zeroth Law of Thermodynamics

Systems are in thermal equilibrium if they do not exchange energy in the
form of heat.
Zeroth Law of Thermodynamics: The zeroth law states that if two
systems are in thermal equilibrium with a third system then they are also in
thermal equilibrium with each other. In other words; Two bodies are in
thermal equilibrium if both have the same temperature
reading even if they are not in contact.

A
B
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Pressure

F
Normal force exerted by a fluid per unit area of the acting surface P =
A

Unit: in SI system N m-2 = [Pa]

In English engineering system: force per square inch (psi)

Example: for vertical column, under the influence of gravity

The force acting on the system is the weight of the fluid

F = W = mg = ( V) g = A h g

F Ahg
Pgh
= =
=
A
A

mg

Other units of pressure:

1 atm = 101,325 Pa = 101.325 kPa = 0.101325 MPa = 760 mmHg

1 bar = 105 Pa = 0.986923 atm
Read Examples 1.2 & 1.3 (p. 8)
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Exercise (1):
The variation of fluid pressure with height is described by the
differential equation:
dP
= - rg
dz
Here, is specific density and g is the local acceleration of gravity. For
an ideal gas, = MPIRT, where M is molar mass and R is the universal
gas constant. Modeling the atmosphere as an isothermal column of
ideal gas at 283.15 K (10C), estimate the ambient pressure in Denver,
where z = 1 (mile) relative to sea level. For air, take M = 29 g mol-1;
values of R are given in App. A.

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Solution

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Important!!

Thermodynamics deals with absolute pressure which is different than the

gauge reading:
Gauge reading = Absolute pressure Atmospheric pressure

Pressure above atmospheric

Pressure gauge reading (+ve)

Atmospheric pressure (1 atm)

Vacuum gauge reading (-ve)
Absolute
pressure
(> atm)

Barometer
reads
atmospheric

Pressure below atmospheric

Absolute pressure less
than atmospheric

Datum (zero pressure)

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Work
W Fdl

W Fl

Force acting through distance:

F = PA
A

Work caused by displacement of a piston,

e.g. compressing a fluid in a cylinder (work is positive)

V t
W -(PA )d
A

W -PdV

V2

W - PdV

V1

Note: V in these equations refers to total volume.

Sign convention:
+W: work done by the

Work is a path function

surrounding on the system:

-W: work done by the system on
the surrounding

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Inexact differential: is path function and depends on the path followed between
the initial state and the final state, denoted by y (= area under the curve ).
Example; work and heat
Exact differential: is a state function and is independent of the path followed
between the initial state and the final state; it just depends on the values of the
function at the initial state and final state, denoted by dy (= y2 y1 )
Example; V, T and P
Remember:
A relation between P and V should be available to determine the work
(graphical or mathematical).
W = area under the curve

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Graphical Representation of Compression and Expansion Processes

2

Compression:
+ve work?

W
b

W
a

For the compression process:

@ state 1; low pressure & high volume
@ state 2; high pressure & low volume
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Expansion:
-ve work?

Engineering
Thermodynamics

Opposite for
expansion
process

1-28

Example:
Gas contained in a cylinder:
Initial pressure and volume: P1 = 200 kPa
V1 = 0.04 m3
Determine the work done for the following cases:
a) The gas was heated under constant pressure until
the volume of the gas increase to V2 = 0.1 m2.
V2

W - PdV
V1

Gas

V2

-P dV

= - P (V2-V1) = 200 kPa (0.1 0.04)m3 = -12 kJ

V1

b) The same initial condition, but the weight removed in such away that the
relationship between P & V can be expressed as PV = constant & V2 = 0.1 m3.
PV
1 1
= 200 (0.04/0.01) = 80 kPa
V2
V2
PV
1 1
W12 - PdV t ; where PV = constant = P1V1 = P2V2 P
V
V

Final pressure: PV
1 1 PV
2 2 P2

V2

V2

PV
dV t
1 1
-PV
ln V 2
dV t -PV
t
1
1
1 1
V 1 = -(200)(0.04)ln(0.1/0.04) = -7.33 kJ
V
V
V1
V1
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W12 -

BUE

b) Same system as in (b) but P & V expressed as PV1.3 = constant.

Consider the general case of: PV n const .
n
n
const
PV
PV
n
n
1 1
2 2
P

PV n const PV
1 1 PV
2 2
Vn
V n
V n
V2

V2

dV t
V 1 n
t
W12 - PdV -const n -const

n
V

V1
V1
const
1 n
1 n
W12
V

V
1
2
1 n

or

For our problem: P2 200 0.04

0.1

W12
BUE

1.3

(60.77)(0.1) (200)(0.03)
1-1.3

Chemical Engineering Dept.

V1

n 1 n
n 1 n
PV
PV
2 2V2
1 1 V1

1 n

PV
2 2 PV
1 1
W12
1 n

V2

60.77 kPa
= - 6.41 kJ

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Heat
Example: Block of hot copper placed in a beaker of cold water:
Hot copper
(High calorie)

Cold water
(Low calorie)

Copper block cools

down and water warms up

Result

Colder copper
worm water
(same calorie)

What causes the decrease and

increase in temperature ?

Definition of heat: form of energy that is transferred across the boundary of the
system at a given temperature to another system (or surrounding) at a lower
temperature by the virtue of temperature difference between the two systems.
High T and low T bodies

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Thermal communication

Thermal equilibrium should be achieved by heat

transfer from high T to a lower T till Tf = Ti
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A body never contains heat

Heat is just crossing the boundary

(like electrical current)

Heat is a transient phenomenon

A body contain energy ( voltage)

Q I
Energy Voltage

Temperature is the driving force for heat flow:

Rate of heat transfer T
When energy in the form of heat is added to a body, it is not stored as heat but
as kinetics or potential energy molecules making up the body
Sign convention:
+Q: heat done by the surrounding on the system:
- Q: heat done by the system on the surrounding

T2

T1

Heat like work, is a path function, or inexact differential Q 1Q 2 f (T )dT

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Iso-Processes
Adiabatic process:

a process with no heat transfer (Q = 0)

Isothermal process: a process with constant temperature entirely

Isobaric process:

a process with constant pressure entirely

Isochoric process: a process with constant volume entirely

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Process Types
Isobaric

constant pressure

Isothermal
Isochoric

constant temperature
constant volume

Adiabatic

no heat transfer (Q = 0)

Q. What process is this?

Ans.

Isobaric

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A
Thermodynamic
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Process formulation using

thermodynamic properties

Final state
Process path
Initial
state

V2

V1

System
(2)
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Thermodynamic cycle: Processes as a result of which a system

returns to its original state, i.e., identical end states.

(a) Two-process
cycle

(b) Four-process
cycle

2
4

2
1

1
V

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Analogy between Heat and

Work

1. Heat and work are both transient phenomena: system never posses heat or
work, but either or both cross the system boundary
2. Both heat and work are boundary phenomena: they are observed at the
boundary of the system and represent energy crossing the boundary
3. Both heat and work are path functions and inexact differential: a path
between initial state and final state should be specified in order to determine Q
or W
4. Sign convention is the same for both heat and work:
+ve: addition of Q or W
-ve : transfer of Q or W

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Kinetics Energy
If a body m, acted upon a force F, is displaced
a distance dl during a differential time dt. The
work done is given by:
but F ma
dW Fdl
but

dW madl
dl
du
dW m
dl m du
dt
dt
integration
or dW mudu

mu 2
mu 22 mu12

W

2
2
2

du
dt

BUE

dl
u

Where u is the velocity of the body

u2

u 22 u12

W m udu m
2
2
u1

mu2 is a kinetic energy

Work done on a body in accelerating it from

initial velocity u1 to a final velocity u2 is equal
to the change in kinetics energy of the body.
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or

1
E k mu 2
2
Unit in SI system:
[Ek] = kg . m2/s2 or N.m = Joules
1-38

Potential Energy
If a body m is raised from an initial elevation Z1 to a final

elevation Z2. The upward force exerted on the body is

mg

equal to its weight. Work required to raise the body is:

dZ

W Fdl mgdZ
W mg ( Z 2 Z 1 ) mgZ 2 - mgZ 1 (mgZ )

Work done on the body in raising it from Z1 to Z2 is equal to the change of the
quantity mgZ
To lower the body, work should be done by the body which is also equal to the
change in mgZ.
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 If the work done on a body in accelerating it or elevating it can be subsequently

recovered, then the body by virtue of its velocity or elevation has the ability to
do the work.
Work accelerating a body is said to produce a change in its kinetic energy, or

mu 2
W E K

Work done on a body in elevating it is said to produce a change in its potential

energy, or

W E P mgZ

Unit of EP in SI system:
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[EP] = kg . m/s2 . m = N . m = Joule

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Exercise (2):
A gas is confined in a 0.47-m-diameter cylinder by a piston, on which
rests a weight. The mass of the piston and weight together is 150 kg.
The local acceleration of gravity is 9.813 m s-2, and atmospheric
pressure is 101.57 kPa.
(a) What is the force in newtons exerted on the gas by the atmosphere,
the piston, and the weight, assuming no friction between the piston
and cylinder?
(b) What is the pressure of the gas in kPa?
(c) If the gas in the cylinder is heated, it expands, pushing the piston
and weight upward. If the piston and weight are raised 0.83 m, what
is the work done by the gas in kJ?
What is the change in potential energy of the piston and weight?

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Solution:

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Conservation of Energy
If a body is given energy when it is elevated, then the body conserves or retains
this energy until it performs the work of which it is capable. An elevated body
allowed to fall freely gains in kinetic energy and loses potential energy.
Potential energy is converted into kinetic energy; or its capability for
doing work remains unchanged, or:
Total W = EK + EP = 0
Or

1
1
2
mu 2 mu 12 mgZ 2 mgZ 1 0
2
2

Other types of mechanical energies: Compression of spring by external force,

energy is stored in the spring; later when the spring expands, it performs this
work or releases this energy by a resisting force spring has capability for
doing work.
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