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

System

Temperature
Pressure

Energy

Measure Of Amount

Heat

Force

Work

1.1 INTRODUCTION
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.

1.1 INTRODUCTION
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

1.2 DIMENSIONS AND UNITS

DIMENSIONS
(= measure of
physical quatity)
FUNDAMENTAL /
PRIMARY
DIMENSIONS

DERIVED /
SECONDARY
DIMENSIONS*

Mass (m), Length (L), Time

(t), Temperature (T), Current
(I) & Amount of matter (mol)

Velocity (v), Energy (E),

Volume (V), Force (F),
Power (P), etc.

Derived dimensions = combination of a few primary dimensions.

Eg: Velocity = Distance/Time = L/t

1.2 DIMENSIONS AND UNITS

UNITS
(= magnitudes assigned
to the dimensions)
FUNDAMENTAL /
PRIMARY UNITS

-accompany primary
dimensions

DERIVED /
SECONDARY
UNITS*
-accompany derived dimensions

2 types of unit systems widely used:

i) English System / United States Customary Systems (USCS)
ii) Metric System, SI (International System)

1.2 DIMENSIONS AND UNITS

Differences of Unit Systems
Fundamental / Derived Dimensions

SI Unit

ES Unit

Mass (m)
Length (L)
Time (t)
Temperature (T)
Ammount of matter (mol)
Velocity (v)
Energy (E)
Volume (V)
Force (F)
Power (P)

kg
m
s
K
kmol
ms-1
J (Joule)
m3
N (Newton)
W (Watt)

lbm, oz
ft, in
s
oC, oF, R
lb mol
ft s-1
Btu, cal
gal
lbf
hp

Pressure

N/m2 (Pascal)

psia, psig

1.2 DIMENSIONS AND UNITS

Multiples and Decimal Fractions of SI units
are designated by prefixes
Standard prefixes in SI units:

Prefix
tera, T
giga, G
mega, M
kilo, k
deci, d

Multiple
1012
109
106
103
10-1

Prefix
centi, c
milli, m
macro,
nano, n
pico, p

Multiple
10-2
10-3
10-6
10-9
10-12

1.3 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.
BOUNDARY
2 types of system:

Closed

system/control mass
Open system/control volume

SYSTEM

SURROUNDING

1.3 SYSTEM
Open system
Also known as control volumes
Both mass and energy can cross the boundary
of a control volume
OPEN
SYSTEM

Mass
Energy

Its volume always fixed but its mass not

necessarily fixed.
Example of open system: compressor, turbine,
pump, nozzle

1.3 SYSTEM
Closed System
Also known as control mass
It has fixed amount of mass and no mass can
cross the boundary.
Energy in theform of heat and work can cross
the boundary
Volume does not have to be fixed.
In special case, when energy is not allowed to
cross the boundary -> Isolated system
Example: Rigid tank, piston cylinder device

1.3 SYSTEM

Mass cannot cross

the boundaries of a
closed system, but
energy can

An example of closed
system with a moving
boundary pistoncylinder device

1.3 SYSTEM
Properties of a system

Any characteristic of a system property.

Intensive
Property

-independent
of
mass of a system
Eg: Temperature T
Pressure P
Density

Extensive
Property

-depend on the size of

a system
Eg: Mass
m
Volume
V
Total Energy
E

PROPERTY

the

1.3 SYSTEM
State and Equilibrium

For a system not undergoing any

change, at this point all the properties
can be measured or calculated
throughout the entire system a set
of properties that completely describes
the condition the state of the
system.
At a given state, all the properties of a
system have fixed values. If the value
of even one property changes, the
state will change to a different state.

m = 2 kg
T1 = 20oC
V1 = 1.5 m3
State 1

m = 2 kg
T2 = 20oC
V2 = 2.5 m3
State 2

1.3 SYSTEM
Equilibrium indicate the State Of Balance.
A System that is in equilibrium
experiences no changes when it is
isolated from its surroundings.
Types of Equilibrium:
Thermal
Mechanical
Phase
Chemical

1.3 SYSTEM

Thermal equilibrium if the temperature is the

same throughout the entire system.
Mechanical equilibrium if there is no change
in pressure at any point of the system with
time.
Phase equilibrium when the mass of each
phase reaches an equilibrium level and stays
there such as water and ice inequilibrium.
Chemical equilibrium if its chemical
composition does not change with time, that
is, no chemical reactions occur.

1.3 SYSTEM
Process, Path And Cycle
Any change that a system undergoes from
one equilibrium state to another process,
and the series of states through which a
system passes during a process the
process path.
Example of process A
compression process in
a piston-cylinder device

1.3 SYSTEM
Quasi-static/Quasi Equilibrium Process.
Process that proceeds in the manner that
the System remains infinitesimally/approx.
close to Equilibrium State at all time.
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.

1.3 SYSTEM

Processes in which one thermodynamic

property is kept constant:
Process
Constant property
Isobaric
Pressure
Isothermal
Temperature
Isochoric/isometric
Volume
Isentropic
Entropy

1.3 SYSTEM
A system is said to have undergone a
cycle if it returns to its initial state at the
end of the process
For a cycle, the initial and final states are
identical.

Process
A
1

Process
B
V

1.4 MEASURES OF AMOUNT / SIZE

Three common measures of amount/size:

Mass,

m
Number of moles, n = m/M
Total volume, Vt

1.5 FORCE

From Newtons second law:

Force = mass x acceleration (F = ma)

Unit: N or kg/ms2 (SI unit), lbf (ES unit)
The Newton, N is defined as
a force required to accelerate
A mass of 1 kg at the rate of
1 meter per second.
F
Acceleration,a

1.6 TEMPERATURE

Temperature - a measure of hotness or

coldness or the energy content of a body.
The temperature difference causes the heat
transfer from a hot body (with higher
temperature) to an another cold body (with a
lower temperature).
When heat is transferred to a body, E T.
Two bodies are in thermal equilibrium when
both of the bodies achieve similar temperature.
Temperature applied in thermodynamic
problems must be in absolute units. Absolute
temperature scale in SI unit is Kelvin and
Rankine in ES unit.

1.6 TEMPERATURE
SI

ES

oC

oF

0oC
100oC

32oF
212oC

Unit
Property
Temperature scale
Absolute temperature scale

Melting point
Boiling point

Relation between temperature scales:

T(oF) = 1.8T(oC) + 32
T(K) = T(oC) + 273.15
T(R) = T(oF) + 459.67
T(R) = 1.8T(K)

(oC to oF)
(oC to K)
(oF to R)
(K to R)

1.6 TEMPERATURE

1.7 PRESSURE

Pressure is defined as the normal force exerted

by a fluid per unit area of the surface
P = F/A = mg/A
Pressure only deal with gas or liquid
SI unit: Pascal(Pa)/Nm-2
ES unit: psi = lbf/in2 (pound-force per square
inch)
psia = pound-force per square inch absolute
psig = pound-force per square inch gage.
Other units: bar, standard atmosphere (atm).

1.7 PRESSURE
Pressure

at any point in a fluid is same in all

directions.
Pressure varies in vertical directions due to gravity
effects but does not vary in the horizontal directions.
Pa

Pa=Pb=Pc
P1

P2

Pc

P3
Pb

P1=P2P3

1.7 PRESSURE
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.
Vacuum Pressure Pressure below
atmospheric pressure.

Absolute P must be used in

Thermodynamics
calculations

1.7 PRESSURE

Pvac = Patm Pabs

Pgage = Pabs Patm

(for P<Patm)

(for P>Patm)

1.7 PRESSURE
Pressure measuring device
Manometer is used to measure small and moderate
pressure differences.
The height of the fluid in the tube represents the
pressure difference between the system and the
surroundings of the manometer which is equal to the
gage pressure:
Patm

Pgage P P1 Patm gh
P1 P2 Patm gh
Pgas Patm gh
Patm atmospheric pressure,
P1 gas pressure in the tank,
density of the fluid in the manometer tube,
h the height of fluid between two points in the U - tube,
g gravitatio nal acceleration 9.8 m/s 2 .

1.8 WORK
Energy

can cross the boundary of a closed system in the form

of heat or work. Therefore, if the energy crossing the
boundary of a closed system is not heat, it must be work.
Work is the energy transfer associated with a force acting
through a distance:

W F .s

Work

is also a form of energy transferred like heat and,

therefore, has energy units such as kJ/kNm
. The
The work done per unit time power and is denoted W
unit of power is kJ/s, or kW.

1.8 WORK
Path function
Work, as heat, is path function its magnitude
depend on the path followed during a process as
well as the end states.
Path
functions have inexact differentials
designated by the symbol - a differential amount
of heat or work is represented by Q or W,
respectively:
2

W W
1

The

12

total work is obtained by adding the

differential amounts of work (W) done along the
way or can represented by the area under the
followed path.

1.8 WORK

Properties, however, are point functions - depend

on the state only, and not on how a system reaches
that state, and they have exact differentials
designated by the symbol d. For eg. a small change
in volume, is represented by dV, and the total
volume change during a process between states 1
and 2:

dV V2 V1 V

The volume change is the

same regardless the path
followed.

1.8 WORK
Mechanical forms of work
In many thermodynamic problems, mechanical
work is the only form of work involved.
Mechanical works is associated with the movement
of the boundary of a system or with the movement
of the entire system as a whole.
Some common forms of mechanical work are:
Boundary work
Accelerational work
Shaft work
Spring work
Gravitational work

1.8 WORK
Boundary Work
One form of mechanical work frequently encountered in
practice is associated with the expansion or compression of
a gas in a pistoncylinder device boundary work when a
body within a system boundary causes a force to its
boundary surface to move.
Expansion work (W=+ve) and compression work (W=-ve) are
categorized as boundary work.
The boundary work can be determined by,
2

Wb Wb Fds
1

This

2
F
Ads PdV
1
A

integral can be evaluated only if we

know the functional relationship between
P and V during the process: P f (V )

1.8 WORK
The area under the process curve on a
P-V diagram is equal, in magnitude, to
the work done during a expansion or
compression process of a closed
system
P

represents the absolute pressure and is

always positive. Hence,
When dV=+ve, Wb=+ve expansion work
When dV=-ve, Wb=-ve compression work
Work is path function each path will
have a different area underneath it
the work done will be different for each
process although the initial and final
states are the same.

1.8 WORK
Net work for a cycle
The cycle shown produces a net
work output because the work
done by the system during the
expansion process (area under
path A) is greater than the work
done on the system during the
compression part of the cycle
(area under path B), and the
difference between these two is
the net work done during the
cycle (the pink area) =Wnet

1.8 WORK
Common processes
Constant Volume/Isochoric/Isometric
If

the volume is constant, dV=0, the boundary work :

2

Wb PdV 0
1

for constant volume process, the boundary work = 0.

1.8 WORK
Constant Pressure/Isobaric
If

the pressure is constant, the boundary work:

2

Wb PdV Po dV Po (V2 V1 )
1

or Wb mPo (v2 v1 )
The

magnitude of the work can also be determined

through the area under the curve of P-V diagram.

1.8 WORK
Constant temperature/Isothermal
If

the temperature of an ideal gas is constant, hence the

equation of state for the ideal gas:
P

And

mRT
V

the boundary work:

2

Wb PdV
1

The

mRTo
V2
dV mRTo ln
V
V1

above equation is applicable for ideal gases only. For real

gases, PV=zmRT should be used.

1.8 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.
During actual processes of real gases, pressure and volume are often
related by PVn=C, (n, C = constants)
2

Wb PdV
1

C
dV
Vn

P2V2 P1V1
, for n 1
1 n

For an ideal gas that undergoing

polytropic process,
2
2 C
Wb PdV
1

Vn

dV

mR(T2 T1 )
, for n 1
1 n
V
mRT ln 2 ,
for n 1
V1

Similar to the
isothermal process
of an ideal gas if
n=1

Example 1.3
A rigid tank contains air at 500kPa and
150OC. As a result of heat transfer to the
surrounding, the temperature and pressure
inside the tank drop to 65OC and 400kPa,
respectively. Determine the work done
during the process.

Example 1.4
A piston cylinder device initially contains
0.07m3 of nitrogen gas at 130kPa and 120 OC.
The nitrogen is now expand politropically to a
state of 100kPa and 100OC. Determine the
boundary work done during this expansion.

1.9 ENERGY

Exist in variable forms : heat, mechanical, kinetic, potential,

electric, magnetic, chemical and nuclear.
Definition: Energy = Force x Distance (Unit = N.m = J)
Total energy, E = Total amount of all forms of energies that
exist in a system.
Specific energy- Total energy based on a unit of mass,
e(kJ/kg)
Total energy can be divided into 2 groups:
1) Macroscopic energies related to motion and the
influence of some external effects such as gravity,
magnetism, electricity, surface tension, kinetic and
potential energies.
2) Microscopic energies related to the molecular structure
of a system. Eg : chemical, nuclear, latent heat, sensible
heat. The sum of microscopic energies- internal energy,
U.

1.9 ENERGY
Microscopic Energy
The sum of microscopic energies internal energy, U.
- Phase change of a system such as
liquid phase changes to gas phase.

- Atom bonding in a molecule in

chemical reactions.
- Strong bonds within the nucleus of
atoms.

1.9 ENERGY
Macroscopic Energy
2 main forms of macroscopic energies:
1) Kinetic energy a system possesses as a result of
its motion relative to some reference frame:
mV 2
(kJ)
KE 2
with, V = velocity of the system relative to a fixed
reference frame.
2) Potential energy a system possesses as a result
of its elevation in a gravitational field.
PE mgz (kJ)
with, g = gravitational acceleration, z = elevation of
the gravity centre of a system.
Other forms of macroscopic energies:
gravity, magnetism, electricity, surface tension.

1.9 ENERGY
Total energy
By ignoring the effects of gravity, magnetism,
electricity and surface tension, hence the total
energy is the sum of kinetic energy, potential
energy and internal energy:
E U KE PE U mV2 mgz (kJ)
Almost all closed systems remain stationary
(KE=PE=0) during a process (unless stated)
stationary systems. Hence, the change in total
energy of a stationary system is equal to the
change of its internal energy:
E U
2

1.10 HEAT
Heat

- A type of energy transfer through a system

boundary due to temperature difference.
Heat has energy units, kJ (or Btu) and denoted by
Q.
Heat transfer per unit mass of a system is denoted
q (kJ/kg) and is determined from:
Q
q
m
The

rate of heat transfer (the amount of heat

transferred per unit time) = the total heat
transferred over some time interval.
The heat transfer rate is denoted Q .
The heat transfer rate has the unit kJ/s (=kW).

1.10 HEAT
3

mechanisms of heat transfer: conduction,

convection and radiation.

1.10 HEAT
A process during which there is no heat
transfer (Q=0) adiabatic process.
There are two ways a process can be
adiabatic: Either the system is well
insulated - only a negligible amount of
heat can pass through the boundary,
or both the system and the
surroundings are at the same
temperature - there is no driving force
(temperature difference) for heat
transfer.
An adiabatic process an isothermal
process. Isothermal process refers to
the temperature of the system that
are the same at different state.

Adiabatic
process when
insulated or
when
Tsystem=Tsurr