KKKR1134 Chemical

Engineering Thermodynamics I

CHAPTER I

BASIC CONCEPTS OF
THERMODYNAMICS
INTRODUCTION
 Greek word: “thermodynamics”

◦ Ability to convert heat to power.

◦ All aspects of energy and energy transfer
including power production / generation,
refrigeration and property relation of
substances.
 BASIC LAWS OF
THERMODYNAMICS

1st Law of 2nd Law of

Thermodynamics Thermodynamics
(=Conservation of
Energy Principles)

Energy has its quality

Energy can change and quantity: a real
from one form to process occurs in the
another form with the decreasing quality of
amount of the energy energy.
kept constant

ENERGY BALANCE ENTROPY BALANCE

APPLICATION OF THERMODYNAMICS

The human body

Air-conditioning Airplanes
systems
Air conditioner Airplanes
/ heater

Human
body

Car
Car radiators Power plants Refrigeration systems

radiator
Power Plants
Refrigeration
system
DIMENSIONS & UNITS
DIMENSIONS
(= measure of
physical quantity)

FUNDAMENTAL DERIVED /
/ PRIMARY SECONDARY
DIMENSIONS DIMENSIONS*

Mass (m), Length (L), Velocity (v), Energy (E),

Time (t), Temperature Volume (V), Force (F),
(T), Current (I) & Power (P), etc.
Amount of matter (mol)
 UNITS
(= magnitudes assigned
to the dimensions)

FUNDAMENTAL
UNIT ASAS / DERIVED /
/ PRIMER
PRIMARY SECONDARY
UNITS UNITS*

-accompany primary -accompany derived

dimensions dimensions
Differences of Unit Systems
Fundamnetal / SI Unit ES Unit
Derived Dimensions
Mass (m) kg lbm, oz
Length (L) m ft, in
Time (t) s s
Temperature (T) K oC, oF, R

Ammount of kmol lb mol

matter (mol)
Velocity (v) ms-1 ft s-1
Energy (E) J (Joule) Btu, cal
Volume (V) m3 gal
Force (F) N (Newton) lbf
Power (P) W (Watt) hp
Pressure N/m2 (Pascal) psia, psig
Standard prefixes in SI units
Prefix Multiple
tera, T 1012
giga, G 109
mega, M 106
kilo, k 103
deci, d 10-1
centi, c 10-2
milli, m 10-3
macro,  10-6
nano, n 10-9
pico, p 10-12
Differences between SI and ES
1) Force (F) = Mass x acceleration
F = ma (kgms-2)
SI unit: newton (N).
ES unit : pound-force (lbf).

2) Weight (W) = a type of force  W=mg (N)

Weight (W)  Mass (m)
(derived) (fundamental)
Mass of a body is constant, but its weight can change depending on
gravitational acceleration (g) that varies with the placement.

3) Work (W) = a form of energy = Force x Distance

1 N.m = 1 J
ES unit: Btu (British Thermal Unit). 1 Btu = energy required to
increase the temperature of 1 lbm of water at 68oF by 1oF.
Other unit : calorie (cal). 1 cal = energy required to increase the
temperature of 1 kg of water at 15oC by 1oC.
Dimensional Homogeneity
In engineering world, all equations must be dimensionally
homogeneous  every term in an equation must have similar
unit.

1) Addition, Subtraction & Equality Operations

Eg : 4 s + 1.9 s
1 kg + 2 lb
2 m + 1.5 ft
10.6 N + 1.4 kgms-2

2) Multiplication & Division Operations

Eg : N X m2

kg x m2
s

N x 1
m
SYSTEMS
 System = a quantity of matter or a region in space
chosen for study. Consists of:
◦ Surroundings
◦ Boundary

 2 types of systems:
◦ Closed systems / control mass
◦ Open systems/ control volumes
CLOSED SYSTEMS
 Also known as control mass.
 Characteristics of closed systems:
◦ Contains a fixed amount of mass and no mass can
across its boundary.
◦ Energy in the form of heat or work can cross
the boundary.
◦ Volume of closed systems does not have to be
fixed.
 In special case, when energy is not allowed
to cross the bondary of closed systems 
isolated system.
CLOSED SYSTEMS

An example of closed system with

Mass cannot cross the a moving boundary  piston-
boundaries of a closed cylinder device
system, but energy can
OPEN SYSTEMS
 Also known as control volumes.
 Characteristics of control volumes:
◦ Both mass and energy can cross its boundary called as
boundary surface.
◦ Its volume always fixed but its mass not necessarily
fixed.
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 = amount of all forms of energies that exist in
a system.
◦ Total energy based on a unit mass, e (kJ/kg):

e E
m

 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.
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:

KE  mv 2
2 kJ

with, v = velocity of the system.

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.
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.
Total Energy
 Neglecting the effects of gravity, magnetism,
electricity and surface tension, hence the total
energy is the sum of KE, PE and U:

E  U  KE  PE  U  mV 2
2  mgz kJ

 Almost all closed systems remain stationary

(KE=PE=0) during a process (unless stated) 
stationary systems.
Summary of Total Energy
ENERGY TOTAL
E=U+KE+PE

Microscopic Macroscopic
energy energy

Internal energy Kinetic energy, KE

U Potential energy, PE
Summary of Systems

SYSTEMS

CLOSED CONTROL
SYSTEMS VOLUMES

Stationary systems
KE=PE=0

Isolated systems
E=0
PROPERTIES OF A SYSTEM
 Any characteristic of a system  property.
 Eg.: pressure P, temperature T, volume V, mass m, viscosity,
thermal conductivity, thermal expansion coefficient,
elevation etc.

PROPERTY

Intensive Extensive
Property Property

-independent of the -depend on the size

size of a system of a system
Eg: Temperature T Eg: Mass m
Pressure P Volume V
Density  Total Energy E
Definitions of few properties
 Density,  = mass per unit volume.

Reciprocal of density specific volume, v (=volume per unit mass)

 Relative density, s or specific gravity (SG) = ratio of the density of

a substance to the density of some standard substance at a specified
temperature (usually water at 4oC, H2O = 1000 kg/m3).

 All extensive properties per unit mass specific properties Eg:

Specific volume v=V/m
Specific total energy e=E/m
Specific internal energy u=U/m
STATE & EQUILIBRIUM
State
 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.
Equilibrium
 Equilibrium  state of balance. In an equilibrium state
there are no unbalanced potentials (or driving forces)
within the system  experiences no changes when it is
isolated from its surroundings.
 Types of equilibrium states:
◦ 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 in
equilibrium.
◦ chemical equilibrium if its chemical composition does not
change with time, that is, no chemical reactions occur.

A closed system achieves thermal equilibrium

PROCESS & CYCLES
Process
 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.
Examples of Processes
 A compression process in a piston-cylinder device:

 Processes in which one thermodynamic property is kept

constant:
Process Constant property
Isobaric Pressure (P)
Isothermal Temperature (T)
Isochoric/isometric Volume (V)
Isentropic Entropy (S)
Cycles
 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.

P
2 Process A

1
Process B

V
PRESSURE
 Pressure = normal force exerted by a fluid
per unit area.

 Pressure only deals with gas or liquid.

Pressure in solids  normal stress.
 Unit SI : Pascal (Pa) = Nm-2
 English System : psi = lbf/in2 (pound-force
per square inch), psia, psig.
 Other units: bar, standard atmosphere
(atm).
 Pressure at any point in a fluid is the same in all
directions.
 Pressure varies in vertical directions due to gravity
effects but does not vary in the horizontal directions.
Absolute pressure, Gage pressure &
Vacuum pressure
 The actual pressure at a given position  absolute pressure -
measured relative to absolute vacuum (i.e. absolute zero pressure).
 Most pressure-measuring devices are calibrated to read zero in the
atmosphere, and so they indicate the difference between the
absolute pressure and the local atmospheric pressure  gage
pressure.

 Pressures below atmospheric pressure (P<Patm) vacuum pressures -

measured by vacuum gages that indicate the difference between the
atmospheric pressure and the absolute pressure:

 Absolute, gage, and vacuum pressures are all positive quantities.

 Must use absolute pressures in thermodynamic problems.
 In ES unit, gage pressure and absolute pressure are differentiated
by their respective units:
Relation between absolute pressure,
gage pressure & vacuum pressure

Pvac = Patm – Pabs Pgage = Pabs – Patm

(for P<Patm) (for P>Patm)
Pressure-measuring devices
 Manometer
 Barometer
 Bourdon Tube
Manometer
 Consists of a glass or plastic U-tube containing one or more
fluids such as mercury, water, alcohol, or oil.
 Measures 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  ρgh
P1  P2  Patm  ρgh
 Pgas  Patm  ρgh

Patm  atmospheric pressure,

P1  gas pressure in the tank,
ρ  density of the fluid in the manometer tube,
h  the height of fluid between two points in the U - tube,
g  gravitatio nal accelerati on  9.8 m/s 2 .
Barometer Figure 1

 Measures atmospheric pressure, hence C

atmospheric pressure also known as
barometric pressure. A h
h
 Consists of a mercury-filled tube W=ghA

inverted into a mercury container that is

open to the atmosphere. B

 Referring to Figure 1: Mercury

Pat
M ercury weight at A  Force due to Patm m

W  Patm A
ρghA  Patm A Figure 2
 Patm  ρgh

with, A  cross - sectional area of barometer tube,

ρ  mercury density,
g  gravitatio nal accelerati on , A1 A2 A3
h  mercury height in barometer tube.

Merkuri
Bourdon Tubes
 Another type of commonly used
mechanical pressure
measurement device.
 Consists of a hollow metal tube
bent like a hook whose end is
closed and connected to a dial
indicator needle.
 Calibrated to read zero, so it
measures gage pressure.
 Modern pressure sensors 
pressure transducers - convert
the pressure effect to an
electrical effect such as a
change in voltage, resistance, or
capacitance.

Types of Bourdon Tubes

TEMPERATURE
 Temperature is one of the thermodynamic
properties - a measure of “hotness” or “coldness”
or the energy content of a body.
 When heat is transferred to a body, E  T.
 Temperature difference causes the heat transfer
from a hot body (with T) to an another cold body
(with T).
 Two bodies are in thermal equilibrium when both
of the bodies achieve similar temperature.
 Similar to pressure, temperature applied in
thermodynamic problems must be in absolute
units. Absolute temperature scale in SI unit is
Kelvin and Rankine in unit ES.
Temperature scales
Unit SI ES
Property
Temperature oC oF

scale
Absolute K R
temperature scale
Freezing / 0oC 32oF
Melting point
Boiling point 100oC 212oC

Relation between temperature scales:

T(oF) = 1.8T(oC) + 32 (oC to oF)
T(K) = T(oC) + 273.15 (oC to K)
T(R) = T(oF) + 459.67 (oF to R)
T(R) = 1.8T(K) (K to R)
Kelvin and Celcius Figure 1
 Magnitude for each part of 1
K and 1C is similar:

      
T K   T2 oC  273.15  T1 oC  273.15 
T K   T  C   T  C 
2
o
1
o

 T K   T  C o

 Similar case with 1 R and 1F :

 
T R   T o F
 SYSTEMATIC PROBLEM SOLVING
Read and understand the requirement of the problem

Draw a simple sketch of the physical system involved,

and list the given and hidden information on the sketch

State any appropriate assumptions and approximations made to

simplify the problem – eg. Ideal gas , Patm= 1 atm, Troom=25oC etc.

Determine the unknown properties at known states necessary to

solve the problem from property relations or tables / figures

Determine the process and sketch the process

on property figures such as P-v or T-v

Apply all the relevant basic physical laws and principles (eg. Mass
balance, energy balance, force balance or entropy balance)

Substitute the known quantities into the simplified relations and

perform the calculations to determine the unknowns

Reasoning, verification and discussion