CLB 20703

Chemical Engineering
Thermodynamics
Chapter 1:
Basic Concepts in Thermodynamics

Objective of Chapter 1
Introduce the students towards some of
the fundamental concepts and definitions
that are used in the study of Engineering
Thermodynamics.
Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Introduction
Stems from the Greek words Therme (Heat)
and Dynamis (Force or Power)

In early 19
th
century: consideration of the
motive power of Heat and the capacity of
hot bodies to produce Work

Today: deals generally with Energy and
with relationships among the properties of
matter
What is Thermodynamics?
Thermodynamics is the Science that deals
with Heat and Work and those properties
of substances that bear a relation to Heat
and Work.
Thermodynamics is the study of the
effects of Work, Heat and Energy on a
System. Thermodynamics is only
concerned with large scale observation.
Scopes of Thermodynamics
First and Second Laws of Thermodynamics

To cope with variety of problems especially
in the calculation of Energy Changes, Heat
and Work requirements for processes

Property Values are essential to application
of Thermodynamics

Development of Generalized Correlations
to provide property estimates in the
absence of data
System in Thermodynamics
Always starts with the identification of a
particular Body Of Matter
This body of matter is called the System
System is a quantity of matter or a region in
space being chosen for study.
Boundary is the one that separates System
from its surrounding. Can be real or
imaginary.



System in Thermodynamics
Open System : Exchange of Energy AND
Matter/Mass.
Closed System : Exchange of Energy but
NOT Matter/Mass.
Isolated System : NOT AT ALL
exchange either Energy or Matter/Mass.
Property in Thermodynamics
Thermodynamic State or Condition is
defined by a few measurable
Macroscopic Properties.
All properties of a System has fixed
values. If one property value change, the
state will change to a different one.
Thermodynamic Properties can be
classified into :
a.) Extensive Properties.
b.) Intensive Properties.
Property in Thermodynamics
a.) Extensive Properties :
Those properties that depends on the
amount of material present.
E.g : Mass and Volume.
b.) Intensive Properties :
Those properties that independent on
the amount of material present.
E.g. : Temperature, Pressure, Density
and Specific Volume.

State And Equilibrium
Equilibrium indicate the State Of Balance.
A System that is in equilibrium
experiences NO changes when it is
isolated from its surroundings.
A System is NOT in Thermodynamic
Equilibrium unless the conditions of all the
relevant types of equilibrium are satisfied.
Types of Equilibrium
a.) Thermal b.) Mechanical
c.) Phase d.) Chemical
State And Equilibrium
a.) Thermal Equilibrium.
The Temperature is the SAME
throughout entire system, i.e. no
temperature difference.
b.) Mechanical Equilibrium.
If there is NO change in Pressure at
any point of the System with time.
State And Equilibrium
c.) Phase Equilibrium.
Mass of each phase reaches an
equilibrium level and stays there.
d.) Chemical Equilibrium.
Chemical composition of substance
DOES NOT change with time, i.e. no
chemical reactions occur.
State And Equilibrium
Quasi-static/Quasi Equilibrium Process.
Process that proceeds in the manner that
the System remains infinitesimally/approx.
close to Equilibrium State at ALL TIMES.
Is a slow and Ideal process that allow the
System to adjust itself internally in order
that properties in one part of the system
do not change any faster than those at
other parts.
Act as a standard.
State Postulate
The state of a System is described by its
properties.
Once a sufficient number of properties are
specified, the rest of the properties
assume certain values automatically, i.e.
specifying a certain number of properties
is sufficient to fix a state.
The number of properties required to fix
the state of a System is given by the State
Postulate.
State Postulate
State Postulate :
The state of a simple compressible
system is completely specified by TWO
independent, Intensive Properties.
Simple Compressible System is when a
System is not under the influence of
external force fields such as electrical,
magnetic, gravitational, motion and
surface tension effects

State Postulate
These external force fields are negligible
for most engineering problems.
The State Postulate requires TWO
Independent Properties specified to fix the
state.
Two properties are independent if one
property can be varied while the other one
is held constant.
Good examples are Temperature and
Specific/Molar Volume
Process, Path And Cycle
Process :
Any change that a System undergoes
from one equilibrium state to another
equilibrium state.
Path :
Consist of series of states through which
a System passes during a process.

Process, Path And Cycle
Cycle :
Occurs when the System RETURNS to its
initial state at the END of the process.
This is the case when the Initial and Final
states are the SAME or overlaps.
Some important terminologies :
a.) Isobaric Constant Pressure.
b.) Isothermal Constant Temperature.
c.) Isochoric Constant Volume.
d.) Adiabatic Constant Heat.


Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Dimensions and Units
The dimensions require the definition of
scales of measure specific units of size

Primary units are codified as the
International System of Units (SI)

Multiples and Decimal Fractions of SI units
are designated by prefixes

Other systems of units (e.g. English
engineering system) are related to SI units
by fixed conversion factors
SI Units and Prefixes
Unit Symbol
second s
meter m
kilogram kg
kelvin K
mole mol
Multiple Prefix Symbol
10
-15
femto f
10
-12
pico p
10
-9
nano n
10
-6
micro
10
-3
milli m
10
-2
centi c
10
2
hecto h
10
3
kilo k
10
6
mega M
10
9
giga G
10
12
tera T
10
15
peta P
Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Measures of Amount / Size
Three common measures of amount/size:
Mass, m
Number of moles, n = m/M
Total volume, V
t

Intensive Thermodynamic Variables:
Independent of size of system
Specific volume, V = V
t
/m
Molar volume, V = V
t
/n
Specific density, = V
-1
= m/V
t

Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Force
From Newtons second law:

Force = mass x acceleration (F = ma)





where g
c
= 32.174 (Ib
m
)(ft)(Ib
f
)
-1
(s)
-2


Force (F) SI EES
Equation F = ma F = ma/g
c
Unit N or kgms
-2
(Ib
f
)
Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Temperature
Four temperature scales:
(i) Kelvin scale (ii) Celsius scale
(iii) Rankine scale (iv) Fahrenheit scale

Relations among temperature scales:
t (C) = T (K) 273.15
T (R) = 1.8 T (K)
t (F) = T (R) 459.67
t (F) = 1.8 t (C) + 32
Temperature (contd)
Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Pressure
Pressure is defined as the normal force exerted
by a fluid per unit area of the surface

P = F/A = mg/A




Pressure (P) SI EES
Unit N m
-2
/Pa (Pascal) (psi)
Pressure (contd)
When using manometers for pressure
measurement, P is also expressed as the
equivalent height of a fluid column

P = F/A
= mg/A
= (AL)g/A
= Lg
Pressure (contd)
Absolute Pressure
The ACTUAL pressure at a given
position. Measured relative to Absolute
Vacuum ( Absolute Zero ).
Gage Pressure
The DIFFERENCE between Absolute
Pressure and local Atmospheric
Pressure.

Pressure (contd)
Vacuum Pressure
Is Pressure BELOW Atmospheric
Pressure.

P
abs
= P
g
+ P
atm
P
vac
= P
atm
- P
abs
Pressure (contd)
Most Pressure Gauges only give readings of
gauge pressures

Absolute P = Gauge P + Atmosphere P

Absolute P must be used in
Thermodynamics calculations
Pressure (contd)
Pressure may vary WITHIN the System
with elevation as a result of Gravitational
Effects.
However, the variation of Pressure as a
result of gravity in MOST Thermodynamic
Systems is relatively SMALL and usually
DISREGARDED.
Outline
Introduction

Dimensions And Units

Measure Of Amount

Force

Temperature


Pressure

Energy

Heat

Work
Energy
Energy can exist in numerous forms :
Thermal, Mechanical, Kinetic, Potential,
Electric, Magnetic, Chemical, Nuclear, etc.
Thermodynamics provides NO information
about absolute value of Total Energy of a
System.
Thermodynamics only deals with
CHANGE of Energy which is what really
matters in Engineering Problems.

Energy
Total Energy = Macroscopic Energy +
Microscopic Energy.
Macroscopic Energy :
A System possesses as a whole with
respect to some outside reference frame.
Examples of Macroscopic Energy :
Kinetic Energy and Potential Energy.
Energy
Kinetic Energy
Work is done when a body accelerates
from velocity of u
1
to u
2
, which is equal to
the change in Kinetic Energy of the body

2
2
1
mu E
K
=
|
|
.
|

\
|
A = =
2 2 2
2 2
1
2
2
mu mu mu
W
Kinetic Energy (E
K
) SI EES
Equation E
K
= mu
2
/2 E
K
= mu
2
/2g
c
Unit N m / J (Joule) (ft Ib
f
)
Energy (contd)
Potential Energy
Work required to raise a body is the
product of force exerted and the change in
elevation from z
1
to z
2

Potential Energy (E
P
) SI EES
Equation E
P
= mzg E
P
= mzg/g
c
Unit N m / J (Joule) (ft Ib
f
)
mzg E
P
=
( ) mzg g mz g mz W A = =
1 2
Energy
Microscopic Energy :
Forms of Energy related to molecular
structure of a System and the degree of
Molecular Activity such as Translational
Kinetic Energy ( Motion ), Rotational
Kinetic Energy and Vibrational Kinetic
Energy ( Attractive/Repulsive ).
Very much independent of outside
reference frame.
Energy
The sum of all the Energies is the Total
Energy, E of the System.
Total Energy, E in kJ while on a mass
basis, e in kJ/kg and on a molar basis in
kJ/kmol.
The sum of all the Microscopic forms of
Energy is Internal Energy, U.
Outline
Introduction

Dimensions and units

Measure of amount

Force

Temperature


Pressure

Energy

Heat

Work
Heat
Energy can cross the Boundary of a
Closed System in two distinct forms :
Work and Heat.
Heat can be defined as :
The form of Energy that is transferred
between two Systems ( or a System and
its Surroundings ) by virtue of a
Temperature Difference.

Heat
Some phrases related with Heat in
common use today :
a.) Heat Flow.
The transfer of Thermal Energy.
b.) Heat Addition.
The transfer of Heat into a System.
c.) Heat Rejection.
The transfer of Heat out of a System.
Heat
d.) Body Heat.
The Thermal Energy content of a body.
Other phrases :
Heat Absorption, Electrical Heating,
Resistance Heating, Frictional Heating,
Gas Heating, Heat of Reaction, Liberation
of Heat, Specific Heat, Sensible Heat,
Latent Heat, Waste Heat, Process Heat,
Heat Sink, and Heat Source.
Heat
Heat is Energy in transition and is
recognized only as it crosses the
Boundary of a System.
Adiabatic Process ( Q = 0 kJ ) :
A process during which there is NO Heat
Transfer.
Adiabatic comes from the Greek word
Adiabatos which means not to be passed.
Heat
There are two ways a process can be
Adiabatic :
1.) The System is well insulated so that
only a negligible amount of Heat can pass
through the Boundary.
2.) Both the System and the Surroundings
are at the SAME temperature and
therefore, NO Driving Force ( Temperature
Difference ) for Heat Transfer.
Heat
Symbol : Q.
Unit : Joule ( J ) or kilo Joule ( kJ ).
Heat Transfer per unit mass, q
q = Q/m ( kJ/kg ).
Rate of Heat Transfer or Power = Q/t
Unit : kJ/s or kilo Watt ( kW ).

Heat
Heat is transferred by three mechanisms:

Mechanism Definition
Conduction The transfer of Energy from the more energetic particles of a
substance to the adjacent less energetic ones as a result of
interaction between particles.
Convection The transfer of Energy between a Solid surface and the
adjacent Fluid that is in motion, and it involves the combined
effects of Conduction and Fluid Motion.
a.) Free ( Natural ) Fluid motion is caused by bouyancy forces induced by density
differences due to the variation of temperature in the fluid.
b.) Forced If the Fluid is forced to flow in a tube or over a surface by
external means such as a fan, pump or the wind.
Radiation The transfer of Energy due to the emission of Electromagnetic
Waves ( or Photons ).
Heat
Finally, it needs to be emphasized that :

Heat always flows from higher temperature
to a lower one
Rate of heat transfer is proportional to the
temperature difference between two bodies
Heat is never stored within a body
It exists only as energy in transit between a
System and its surroundings just like Work.
Outline
Introduction

Dimensions and units

Measure of amount

Force

Temperature


Pressure

Energy

Heat

Work
Work
Energy Transfer
If the Energy crossing the boundary of a
CLOSED system is NOT Heat, it must be
WORK.
There will be work when there is
movement. If there is no movement, no
work is done.



Work
Identify weather the situation below are
work or not.
- A teacher applies a force to a wall and becomes
exhausted.
- A book falls off a table and free falls to the
ground.
- A Waiter carries a tray full of meals above his
head by one arm straight across the room at
constant speed.
- A rocket accelerates through space.
Work

Work
Work is force acting through a distance.

s F W . =
Unit, kJ
Work
Work done per unit time is POWER

Power = W/t = ( Fs )/t

(unit kJ/s or kW)
Work
W is performed whenever a force acts
through a distance


W is positive when the displacement is in
the same direction as the applied force or
vice versa

dl F dW =
Work (W) SI EES
Unit N m / J (Joule) (ft Ib
f
)
Work (contd)
W is also performed when there is a
change in volume of fluid (compression or
expansion)




The minus sign is required because the
volume change is negative
A
V
d PA dW
t
=
t
dV P dW =
}
=
t
t
V
V
t
dV P W
2
1
Work (contd)
Work
Moving Boundary Work.
The work associated with a Moving
Boundary is called Boundary Work.

Therefore, Expansion and Compression
Work is often called as Moving Boundary
Work.

Work

The moving boundary
Work

air
Compression process
- dV ve, - W


air
Work
Expansion process
- dV +ve, W
Work
Moving Boundary Work
Total Boundary Work done
during the entire process as
the piston moves is obtained
by adding all the differential
works from the Initial to Final
state.
W = Fds = PAds = PdV
Work
Moving Boundary Work

Total boundary work from initial state to final state
}
=
2
1
PdV W
Work
Area under curve = PdV=Work
Work
Isochoric Process
Constant Volume

Work

Isobaric Process
Work

Work
Polytropic Process
A process which occurs with an
interchange of both heat and work
between the system and its surroundings.
The non-adiabatic expansion or
compression of a fluid is an example of a
polytropic process.

Work
Polytropic Process

Work
Polytropic Process

Work,

Work
Isothermal Process

Work
Isothermal Process

2 ln
ln ,
1
2
1 1
V P W
V
V
V P W Work
=
=
Work
Other Mechanical Forms Of Work :
a.) Gravitational Work :
Work Done by Gravitational Force.
b.) Acceleration Work :
Work Done by ordinary Force.
c.) Shaft Work :
Work Done by Rotating Shaft.
d.) Spring Work :
Work Done by expansion of spring through some
displacement.

Work
Non Mechanical Forms Of Work :
a.) Electrical Work :
Work Done as a result of Voltage/Electrical Potential
and Electrical Charge.
b.) Magnetic Work :
Work Done by Magnetic Field Strength and Total
Magnetic Dipole Moment.
c.) Electrical Polarization Work :
Work Done by Electrical Field Strength and Polarization
of the Medium.
Energy Conservation
Work done on a body is equal to the
change in a quantity of Energy




Work performed can be recovered by
carrying out reverse process and returning
the body to its initial condition
( ) mzg E W
P
A = A =
|
|
.
|

\
|
A = A =
2
2
mu
E W
K
0 = A + A
P K
E E
Energy Conservation (contd)
Work is energy in transit, not residing in a
body, and can be converted into another
form of Energy

Work exists only during energy transfer
from the surroundings to the system, or the
reverse

In contrast, Kinetic and Potential Energy
reside within the system