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UEMK2113Chemical
EngineeringThermodynamics
Lecturer:PangYeanLing

MarksAllocation
COURSEWORKS:
1Test:20%,Assignment:20%

FINALEXAMINATION:60%

PASSINGMARK:50%

Textbook
1. Koretsky,M.D.(2004)Engineeringand
ChemicalThermodynamics,1stedition,John
Wiley&Sons.(ISBN:0471385867)
(NewEdition)Koretsky,M.D.(2013)
EngineeringandChemicalThermodynamics,
2ndedition,JohnWiley&Sons.

2. SmithJ.M.,VanNessH.C.,Abbott
M.M.(2004)IntroductiontoChemical
EngineeringThermodynamics,7thEd.Mc
GrawHill(ISBN:0072402962)

CONSULTATIONHOURS:
Monday:10am12pm;1pm3pm
Thursday:10am12pm;2pm4pm

*pleasemakeappointmentatleast2daysprior
totheconsultation
Email:pangyl@utar.edu.my

*tutorialclassstartingweek2
*noclassduringCNYweek(week6)
*tutorialclass(6.3.15)10.30am12.30pm
Venue:fromSD206changetoSA229

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CHAPTER1
Introduction

Application areas of Thermodynamics

Applications:
SteamPowerPlant(Togenerateelectricity)
FuelCells
VapourCompressionRefrigerationCycle(Air
Conditioning)
TheAirSeparationPlant
TheGasTurbine(AirplaneFlying)
GasMixtures(Separation)
ChemicalReactions(Fuelburning,Chemical
Production)

LawsofThermodynamics

1ZerothLawofThermodynamics
2.FirstLawofThermodynamics
3.SecondLawofThermodynamics
4.ThirdLawofThermodynamics

ZerothLaw
Thezerothlawofthermodynamicsstatesthat
whentwobodieshaveequalityof
temperaturewithathirdbody,theyinturn
haveequalityoftemperaturewitheachother

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Temperature and 0th Law of Thermodynamics

The zeroth law of thermodynamics states that if 2 bodies are in


thermal equilibrium with a third body, they are also in equilibrium
with each other.
If the third body is a thermometer, the zeroth law of
thermodynamics implies that 2 bodies are in thermal equilibrium if
they have the same temperature even if they are not in contact.

1stlawofThermodynamics
ConservationofEnergy

Temperature scales are based on easily reproducible states such as


ice point and steam point. In Celsius scale, ice point is 0C and steam
point is 100C. In Fahrenheit scale, ice point is 32F and steam point
is 212F.
A thermodynamic temperature scale (derived from the second law
of thermodynamics) is independent of the substance used. Lowest
temperature is 0 K or -273.15C.

Thermodynamics and Energy (1)

1stLaw

Thermodynamics is the science of energy. Energy is the ability to


cause changes.
The First Law of
Thermodynamics is simply an
expression of the conservation
of energy principle i.e. energy
cannot be created or
destroyed. Hence, during an
interaction, energy can change
from one form to another but
the total amount remains
constant.

2ndLaw
2ndlawofthermodynamics

TheKelvinPlanckstatement:
Itisimpossibletobuildanenginewhich
operatinginacyclecanconvertalltheheatit
absorbsintowork.

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Thermodynamics and Energy (2)

3rdLaw

The Second Law of Thermodynamics asserts that energy has


quality as well as quantity.

3rdlawofthermodynamics
TheentropyofaperfectcrystalisZEROat
absolutezerotemperature

dS=(dQ/T)rev

Actual processes occur in the direction of decreasing quality of


energy.

Definition - Systems

1N=1kgm/s2
1Pa=1N/m2
1bar=10Pa=0.1Mpa
1atm=101325Pa
=14.7psi
g=9.806m/s2=32.174ft/s2
K=C+273.15
R=F+459.67

A system is a quantity of matter or a


region in space chosen for study.
Everything external to the system is
the surroundings, with separation by a
real or imaginary boundary (fixed or
movable).
A system may be closed or open. A closed
system (or control mass) contains a fixed
amount of mass, but volume can change.
No mass can enter or leave, but energy (in
the form of heat or work) can cross the
boundary.
An isolated system has no energy
transfer across the boundary.

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Definition Control Volumes

An open system (or control volume) is a selected region in space.


Any arbitrary region can
be selected, but the
proper choice would make
the analysis easier.

The boundaries of a control


volume is called a control
surface.
Beside heat and work, a control volume has flow of mass into it,
out of it, or both.

State, State Postulate and


Equilibrium
A state is a condition determined by a
certain number of properties. Each
property has a definite value at a given
state, independent of its prior history.
In the absence of electrical, magnetic,
gravitational, motion, and surface tension
effects, the state postulate requires 2
independent, intensive properties to fix the
state.
Thermodynamic equilibrium (e.g. thermal, mechanical, phase and
chemical)of a system is a condition in which every property is
uniform throughout, hence there are no unbalanced potentials within
a system.

Properties of a System

A property is any observable macroscopic characteristic of a


system e.g. pressure P, temperature T, volume V, and mass m.

Properties are considered to be either


intensive or extensive.
Intensive properties are those that are
independent of mass, e.g. T, P, .
Extensive properties depend on mass e.g.
volume, momentum, mass.
Extensive properties per unit mass are called
specific properties e.g. specific volume v =
V/m, specific energy e = E/m

Processes and Cycles


A process is a change undergone by a
system from one equilibrium state to
another. The series of equilibrium
states undergone is called path of the
quasi-equilibrium process.

A nonquasi-equilibrium process does not


have a single state at any stage and hence
cannot be described by a process path.
A process in which a particular property remains constant is
designated with the prefix iso. Examples are isothermal, isobaric,
and isochoric (isomeric) processes.
A system is said to have undergone a cycle if it returns to its initial
state at the end of a sequence of processes.

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Steady-Flow Processes

A steady-flow process is a process during which a fluid flows


through a control volume steadily.

Fluid properties can change from point


to point within the control volume (i.e.
not necessarily uniform), but at any
fixed point they remain the same
during the entire process.

Ideal-gas temperature scale

A good approximation to the thermodynamic scale within certain


range of temperature is the ideal-gas temperature scale.
At low pressures, gas temperature is
proportional to pressure.
So, a constant-volume gas thermometer
may be interpreted to read 0 K or 273.15C at zero pressure.

Steady flow conditions can be closely approximated by continuously


operating devices e.g. turbines, pumps, boilers, condensers etc.
Cyclic or pulsating devices e.g. reciprocating engines can be treated
as steady-flow as well by using time-averaged properties.

Pressure

Internal Energy

Internal energy is the sum of several forms of


microscopic energy involving the molecules i.e.
sensible, latent, chemical and nuclear.

Many thermodynamic equations involve working in absolute pressure.


Relationship between absolute, gauge and vacuum pressures is shown
in the diagram.

Sensible energy is the component of internal energy


associated with kinetic energies of the molecules
from different types of motion. Higher temperature
produces faster motion and hence higher sensible
energy.
Latent energy is the component of internal energy
associated with the phase of a substance. The gas
phase has higher latent energy than in the liquid or
solid phase because energy has been added to
break the binding forces.

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Forms of Energy

Total energy E of a system may include different forms e.g.


thermal, mechanical, kinetic, potential, electric, magnetic, chemical
and nuclear.

These various forms of energy may be classified as macroscopic (i.e.


taken as a whole with respect to certain reference frame e.g.
kinetic, potential) or microscopic (i.e. related to molecular structure
and activity, e.g. thermal, chemical, nuclear). Sum of all microscopic
energies is called internal energy U.

If magnetic, electric and surface tension effects are negligible,


total energy of a system is
E U KE PE U m

Mechanical Energy

For control volume,

V2
mgZ
2

or

e u

V2
gZ
2

V
gZ
E m e m u
2

During an interaction, energy can cross the boundary of a


closed system by heat or work.
Heat is a form of energy in transition. It is
transferred between 2 systems (or a system
and its surroundings) by virtue of
temperature difference.
Heat can be transferred by 3 mechanisms:
conduction, convection and radiation.

Kinetic and potential energies are forms of mechanical energy.


Thermal energy is not mechanical energy as it cannot be converted
completely and directly due to constraints imposed by Second Law
of Thermodynamics.
Another form is flow energy due to pressure force acting on a fluid
through a distance. Flow work per unit mass is P/.
Hence, rate of mechanical energy in a flowing fluid is
2

emech m
P V gz
Emech m
2

Energy Transfer by Heat or


Work (1)

Mechanical energy is the form of energy that can be converted to


mechanical work completely and directly by an ideal mechanical
device.

Energy Transfer by Heat or


Work (2)

Work is also energy in transition. If energy crossing the boundary of


a closed system is not driven by temperature difference (i.e. heat), it
must be work.
By normal convention, heat transfer to a system and work done
by a system are positive; heat transfer from a system and work
done on a system are negative.

Alternatively, sign for heat and work can be


ascertained by specifying direction.

An adiabatic process is a process with no heat


transfer.

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Energy Transfer by Heat or


Work (3)

Mechanical and Nonmechanical Forms of Work (1)

In thermodynamics, heat and work are energy transfer mechanisms


between a system and its surroundings.

Both are recognized at the boundaries of a system as they cross

Shaft power

2NT
W
sh

the boundaries i.e. boundary phenomena.

Spring work

Wspring

1
k x22 x12
2

Systems possess energy, but not heat or work.


Both are associated with a process, not a state.
Unlike properties, heat or work has no meaning
at a state.

Both are path functions i.e. their magnitudes

depend on the path followed during a process as


well as the end states.
Path function

W W

12

Welastic nAdx
1

Power to raise
a body

mgV
W
g
Wa

Surface tension work


2

Wsurface sdA
1

Energy Conversion Efficiencies

Work to
accelerate a
body

Electrical
power

VI
W
e

Efficiency indicates how well an energy conversion or transfer


process is accomplished.
In general,

Efficiency or Performance

1
mV22 V12
2

i.e. not W2 W1

Mechanical and Nonmechanical Forms of Work (2)

Elastic work

Desired output
Required input

Combustion efficiency

combustion

Heat release rate


Q

Mass x heating value of fuel m HV

HV is called lower heating value (LHV) when water remains as


vapour in the combustion gases.
HV is called higher heating value (HHV) when water is completely
condensed in the combustion gases.

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First Law of Thermodynamics (2)

The net change (increase or decrease) in the total energy of a


system during a process is equal to the difference between the total
energy entering and total energy leaving i.e.

First Law of Thermodynamics (3)

Rate form:
Examples

Win Wout

Emass,in Emass,out
5 kJ

Esystem U KE PE Qin Qout Win Wout

Esystem Qin Qout

Emass,in Emass,out

Win Wout

Emass,in Emass,out

U2 800 400 400 kJ

153 12kJ

Esystem Ein Eout Qin Qout Win Wout Emass,in Emass,out

Wnet ,out Qnet ,in

8 kJ

5 kJ

U KE PE

For a closed system undergoing a cycle,

Ein Eout

Emass,in Emass,out

Emass,in Emass,out

First Law of Thermodynamics


(5)

Win Wout

Win Wout

dEsystem
Ein Eout
dt

Esystem Qin Qout

Esystem Qin Qout

Esystem Qin Qout

Ein Eout Esystem

Qin Qout Win Wout Emass,in Emass,out

Examples

Energy and Environment (1)


Combustion of fossil fuels (oil, coal and natural
gas) produce pollutants that cause smog, acid
rain, global warming and climate change.

The major air pollution source is the

motor vehicle. Their emissions include HC,


NOx, CO, CO2 and PM. Car emission has
decreased steadily over the years: HC
emission was 5 gpkm in 1970, 0.25 gpkm in
1980 and 0.06 gpkm in 1999. HC emission is
due to fuel spillage, evaporation during
refuelling, evaporation and leakage to
atmosphere by faulty fuel caps.

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Energy and Environment (2)

Smog is a dark yellow to brown


haze made up of ground level ozone
but it may contain traces of CO, HC,
PM. (note: Upper atmosphere ozone
layer protects the earth from suns
harmful UV radiation).
Ground level ozone (and therefore
smog) is produced when HC and NOx
react under the effect of sunlight and
heat.

Energy and Environment (3)

Acid rain is produced when SOx and


NOx react with water vapour under the
influence of sunlight and heat to form
sulfuric and nitric acids.
Excessive SOx and NOx emissions from
electricity generation facilities are
beyond soils ability to neutralise them.
SOx emissions are reduced by installing
scrubbers and/or by desulfuring coal
before combustion.

Energy and Environment (4)

Entropy

Ordinary glass is transparent to short

wavelength (visible light) radiation, and


opaque to long wavelength (infrared)
radiation. Greenhouse effect causes
global warming and global climate change.

The major greenhouse gas is CO2.


Normally, plants absorb CO2 during
photosynthesis and release O2 to maintain
a satisfactory level of CO2 and O2 in the
atmosphere. Excessive CO2 emissions
have adversely affected this balance.

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Entropy (2)

For the reversible case,

Q
dS 0

T int rev

Entropy (3)

S is a thermodynamic property called


entropy (by Clausius). Recall that a
thermodynamic property is a quantity
whose cyclic integral is zero. It
depends on the state only, and not
the process path.

Entropy can be viewed as a measure


of molecular disorder or molecular
randomness. The level of molecular
disorder increases as it melts or
evaporates.

The change in entropy between 2 states is given


by the integral of Q/T along an internally
reversible path.

A pure crystalline
substance at absolute zero
temperature is in perfect
order, and its entropy is
zero. This is known as the
third law of
thermodynamics.

T int rev

To find entropy change of a irreversible

process, integrate Q/T along a convenient


imaginary path which is internally reversible.

Entropy (4)

Entropy (2)

Example 1: Entropy change in isothermal process

Given: 750 kJ of heat is transferred to liquidvapour mixture of water.


Process is isothermal at 300 K (& isobaric).

For the reversible case,

Q
dS 0

T int rev

Find: Entropy change


Noting that isothermal heat transfer process is
internally reversible, hence

1
Q

T int rev To

Q
1

int rev

Q
To

750
2.5 kJ/K
300

S is a thermodynamic property called


entropy (by Clausius). Recall that a
thermodynamic property is a quantity
whose cyclic integral is zero. It
depends on the state only, and not
the process path.

The change in entropy between 2 states is


given by the integral of Q/T along an
internally reversible path.

T int rev

To find entropy change of a irreversible

process, integrate Q/T along a convenient


imaginary path which is internally reversible.

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Phase-change Processes of Pure Substances (1)

Phase-change processes occur in many situations e.g. water steam in


a boiler, steamwater in a condenser, liquidvapour refrigerant in a
refrigerator etc.

Phase-change Processes of Pure Substances (2)

Continue to add heat,

Consider heating water at 20 C in a container at 1 atm.,


Add

Add

heat

heat

Saturated liquidCompressed or subcooled Saturated liquid


liquid (i.e. liquid not about (i.e. liquid about to vapour mixture
(i.e. liquid and vapour
vapourise)
to vapourise)
phases coexist).

Saturated liquidvapour mixture


(i.e. liquid and
vapour phases
coexist).

Add

Add

heat

heat

Superheated vapour
Saturated vapour
(i.e. vapour not about
(i.e. last drop of liquid
just vaporised or vapour to condense)
about to condense)

Phase-change Processes of Pure Substances (3)

Phase-change Processes of Pure Substances (4)

The heating process of water at 1 atm. pressure (i.e. 101.325 kPa)


is shown in the following T-v diagram

Saturation temperature Tsat and saturation pressure Psat are


dependent properties.

Saturation pressure
(i.e. pressure at which a
pure substance changes
phase)
Saturation temperature
(i.e. temperature at
which a pure substance
changes phase)

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Phase-change Processes of Pure Substances (5)

Phase-change Processes of Pure Substances (6)

Variation in saturation temperature with saturation pressure may


also be seen in a T-v diagram.

Saturation temperature

increases with pressure.

T-v
diagram

At 22.06 MPa, saturated

A large amount of heat is absorbed or released during a phasechange process.

Latent heat of fusion is the amount of heat required to melt unit

mass of a solid, or equivalently the amount of heat released during


freezing.

Latent heat of vaporization

is the amount of heat required to


vaporize unit mass of a liquid, or equivalently the amount of heat
released during condensation.

liquid and saturated vapour


states are identical. This is
called the critical point.

Note: Latent of heat of vaporisation decreases with


temperature.

Above the critical point,

liquid and vapour cannot be


distinguished from one
another.

Property Diagrams for Phase-change Processes (1)

Regions for different phases of a pure substance may be represented in Tv, P-v, P-T and P-v-T diagrams.

Connecting the saturated


liquid and vapour points
produces the saturated
liquid line and saturated
vapour line respectively.

To the left of saturated

liquid line is the compressed


liquid region and to the right
of the saturated vapour line
is the superheated vapour
region. In between the 2
saturated lines is the wet (or
mixed) region.

T-v
diagram

Property Diagrams for Phase-change Processes (4)

The P-T diagram is often


called the phase
diagram.

The lines of sublimation

(solidvapour), vaporization
(liquidvapour) and melting
(solidliquid) meet at the
triple point.

P-T
diagram

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Property Tables (2)

For saturated liquid and vapour states of water,

Table A-4: Temperature Table


Table A-5: Pressure Table
Subscripts
f Saturated liquid value (vf)
g Saturated vapour value (vg)
fg Difference between saturated
vapour and saturated liquid
values (vfg)
where vfg = vf - vg

Property Tables (4)


For saturated liquid-vapour mixture,
Quality (x) is the ratio of

mass of vapour to the total mass


of the mixture.

v vf
vfg

mg
mf mg

u uf
ufg

h hf
hfg

s sf
sfg

x has meaning only in the


wet region and can take
values between 0 and 1,
and has no meaning outside this
region or range.

Ideal-gas Equation of State

Property Tables (8)

Reference State
Values of properties u, h and s are always given with respect to a
reference state of zero value. For water, at 0.01 C, u = 0 and s = 0.
For refrigerant R-134a, at -40 C, h = 0 and s = 0.

Equation of state describes the correlation between P, v and T.

The ideal gas equation of state is:

P v = RT or PV =m RT
where R is the specific gas constant equal
to the universal gas constant (=8.3145
kJ/kmol-K) divided by the molecular
weight of the substance. For air
R=8.3145/29=0.287 kJ/kg-K.

Water vapour can be treated as an

ideal gas only at low pressures.


Significant error can be found if used
near the critical point, and at high
pressures.

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Tutorial1
Tutorial1:
No.2.1,2.9,2.52,2.53,2.54,3.5
(Koretsky,M.D.(2004)EngineeringandChemicalThermodynamics,1st
edition,JohnWiley&Sons)

No.2.18,2.23,2.77,2.78,2.79,3.21
(Koretsky,M.D.(2013)EngineeringandChemicalThermodynamics,2nd
edition,JohnWiley&Sons)

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