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General

Engineering and
Applied Sciences

Thermodynamic
s
Presented by:
Engr. Jefril M. Amboy

Part I
Basic Concepts,
Temperature and Heat

What is Thermodynamics?

THERMODYNAMICS
is the science of
energy!
Thermodynamics is the study of
the transformation of heat,
mechanical work and other forms
of energy and how these
transformations relate to
properties of matter.

Etymology

Thermodyna
mics
therm dynam
e
is
heat

power

Divisions of Thermodynamics

Thermodyna
mics
classic statistic
al
al
microscopic

macroscopic

The System and Its


Surroundings
A system is defined as a quantity
of matter or a region in space to
be studied.
The mass or region outside of the
system is called the surroundings.
The real or imaginary surface that
separates the system from its
surroundings is called the
boundary.

System, Surroundings and


Boundary

Types of Systems
A closed system is composed of a
fixed amount of mass and no
mass can cross its boundary.
If both mass and energy are not
allowed to cross the boundary,
the system is said to be isolated.
An open system allows the
transfer of both mass and energy
across a boundary.

A Closed System (Control


Mass)

Mass cannot cross the


boundary of a closed system,
but energy can.

An Open System (Control


Volume)

A control volume with moving


and fixed boundaries.

Properties of a System
Any characteristic of a system is
called a property. Properties can
be intensive or extensive.
If a property is independent of the
mass of the system, it is an
intensive property. Otherwise, it
is extensive.
Extensive properties per unit
mass are called specific

The State of a System


The state of a system refers to its
conditions which can be described
completely by its properties.
A system is said to be in
thermodynamic equilibrium if
maintains thermal, mechanical,
phase and chemical equilibrium.

What is a Process?
A process refers to any change in
the state of a system. A process
that starts and ends with the
same state is called a cycle or
cyclic process.
A system is said to be in
thermodynamic equilibrium if
maintains thermal, mechanical,
phase and chemical equilibrium.

Processes and Cycles


A process refers to any change
that a system undergoes from one
equilibrium state to another.
The series of states that the
system has undergone during a
process is called the path of the
process.

Temperature
Temperature maybe regarded as
the quantitative measure of the
hotness or coldness of a body.
Statistically, temperature is
defined as the measure of the
average kinetic energy of all the
molecules that make up a
material.

Thermal equilibrium
A condition in which the
temperature of a system is the
same and equal to the
temperature of its surroundings is
called thermal equilibrium.
Two bodies are in thermal
equilibrium if they are at the
same temperature, whether or
not they are in physical contact.

The Zeroth Law of


Thermodynamics
The zeroth law of thermodynamics
states that if two bodies are in
thermal equilibrium with a third
body, they are also in thermal
equilibrium with each other.
Two bodies can be in thermal
equilibrium with each other even
if they are not in physical contact
with each other.

Temperature Scales
Temperature scales are used as
the basis for measuring
temperature.

Common Temperature
Scales

Celsius
Fahrenhei
t

Kelvin
Rankine

Temperature Conversions
TC 10
5
=
=
TF 0
9
18
0
9
TF = TC +
5
32
5
TC = (TF
9
32)

The Thermodynamic
Temperature Scale
A temperature scale that is
independent of the properties of
any materials is called a
thermodynamic temperature
scale.
The thermodynamic temperature
scale in the SI system is the
Kelvin scale. In the English
system, it is Rankine scale.

The Ideal Gas Temperature


Scale
A temperature scale that is nearly
identical to the Kelvin scale is the
ideal-gas temperature scale.
Temperatures in this scale are
measured using a constantvolume gas thermometer.

The Development of the


Kelvin Scale

TK = TC +
273.15
Absolut
e zero!

The Kelvin Scale


The Kelvin scale is considered as
the absolute
scale. It
One
kelvin is temperature
defined as 1/273.16
is
on two fixed
of based
the difference
between the
temperatures
theabsolute
triple
point of namely
water and
absolute zero and the triple point
zero.
of
water.
Absolute zero: 273.15C = 0

K
Triple point (H2O): 0.01C =
273.16 K

Thermal Expansion
The expansion of a material when
heat is applied is called thermal
expansion. Properties like length
and volume are affected by
temperature changes.

LL
T

o
VV
To

Example:
Jim uses a steel measuring tape
that is exactly 50.000 m long at
an ordinary temperature of 25C.
What is the length of the steel
tape on a hot summer day when
the temperature gets 35C?

Ans: 50.006
m

Thermal Stress
The expansion or contraction of
materials due to temperature
changes may result to thermal
stress , which is analogous to
pressure (force per unit area).

= ET

Example:
A cylindrical aluminum having a
radius of 2.5 cm is used as a
spacer between two steel walls
such that the two bases of the
cylinder are touching the walls. At
17C, the cylinder just slips in
between the walls. When it warms
to 25C, calculate the stress in the
cylinder
and kN
the force that it
Ans: 26.4
exerts on each wall, Assuming

Heat
Heat is defined as
the transfer of
thermal energy
across a boundary
or from one body to
another due to
temperature
difference between
them.

The Unit of Heat


Since heat is a transfer of energy,
it has the same unit as energy.

joule
calorie
BTU

1 BTU =
1055 J

The Mechanical Equivalent of


Heat

1 cal =
4.186 J

Unit Conversions for Heat


1 cal =
4.186 J
1 BTU = 1055 J
1 BTU = 252
cal
1 BTU = 778
ft-lb

Sensible Heat
The amount of heat required to
change the temperature of a
given mass of a pure substance is
called sensible heat. This amount
of heat Q is directly proportional
to the mass m of the substance
and to the change in temperature
T.

Q=
mcT

Specific Heat
The specific heat is defined as
that amount of energy transferred
by heat necessary to change
temperature of a given unit of
mass by 1 C.

Q
c
mT

J/kg K

Specific Heat of water


c 4.186 J/g C
c 4,186 J/kg K
c 1 cal/g C
c 1 BTU/lb F

Heat Capacity
The heat capacity of a substance
is the amount of energy needed to
raise the temperature of a given
sample by 1C.

Q
C
T

J/K

Molar Heat Capacity


The molar heat capacity of a
substance is the product of its
specific heat and molar mass.
Determine the molar heat
capacity of water.

Ans: 75.35 J/mol


K

Dulong-Petit Law
The law of Dulong and Petit states
that the molar heat capacities of
most elemental solids approach
the value 3R, which is
approximately 25 J/molK.

Phase Changes
A transition from one state of
matter to another is called a
phase change. At a given
pressure, a substance changes
from one phase to another at a
definite temperature. More
importantly, the phase change is
always accompanied by the
absorption or release of energy,
usually by heat.

Latent Heat
Latent heat is the amount of
energy transfer needed to change
the phase of a given mass of
substance without changing its
temperature.

Q = mLf
Q=
mLv

for water:
Lf = 80
cal/g
Lv = 540

Calorimetry
Calorimetry is all about heat
calculations involved in various
physical changes.
When energy is transferred by
heat between two bodies, the
heat lost by one body equals the
heat gained by the other.

Qlost = Qgained

Example:
A 0.050 0-kg ingot of metal is
heated to 200.0C and then
dropped into a calorimeter
containing 0.400 kg of water
initially at 20.0C. The final
equilibrium temperature of the
mixed system is 22.4C. Find the
specific heat of the metal.

Ans: 453 J/kg


K

Example:
A cowboy fires a silver bullet with
a muzzle speed of 200 m/s into
the pine wall of a saloon. Assume
all the internal energy generated
by the impact remains with the
bullet. What is the temperature
change of the bullet? For silver c
= 234 J/kgC

Ans: 85.5C

Example:
Determine the total amount of
energy needed to convert 250 g of
ice at a temperature of 10C to
steam at 120C.

Ans: 769 kJ

Example:
What mass of steam initially at
130C is needed to warm 200 g of
water in a 100 g glass container
from 20.0C to 50.0C?

Ans: 10.9 g

Energy Transfer Mechanisms


There are three mechanisms on
how energy can be transferred by
heat in thermal processes:

conductio
n
convectio
n
radiation

Thermal conduction
Conduction is the process by
which energy is transferred by
heat as a result of interaction
among particles. The transfer of
energy occurs when the particles
gain kinetic energy in collision
with more energetic particles.
The gain in KE results to a change
in temperature.

Law of Thermal Conduction


The rate at which energy is
transferred by thermal conduction
is proportional to the temperature
gradient.

dQ
T
H
kA
dt
x

H = heat current in watts

Law of Thermal Conduction

Th Tc
dQ
H
kA

dt
L

Example:
A cooler made of Styrofoam has a
total wall area of 1.2 m2 including
the lids and a wall thickness of 1
inch. The cooler is filled with lots
of ice and bottled beers. What is
the rate of heat flow into the
cooler if the air outside has a
temperature of 27C? How much
Ans:
12.7
J/s,day?
3.3
ice
melts
in one

kg

Convection
Convection is an energy transfer
mechanism which involves the
combined effects of conduction
and fluid motion. In convection,
there is a transfer of fluid mass
from one region of space to
another.

Convection
The rate of heat transfer by
convection is determined from
Newtons law of cooling.

dQ
H
hAT
dt

Example:
Consider a person standing in a
breezy room at 20C. Determine
the total rate of heat transfer
from this person if the exposed
surface area and the average
outer surface temperature of the
person are 1.6 m2 and 29C,
respectively, and the convection
2
heat
transfer
coefficient
is
6
W/m
Ans: 168.1
C

Radiation
Radiation is the energy transfer
by means of electromagnetic
waves. It does not require any
physical contact or medium, and
thus, radiation can take place
even in a vacuum.
Thermal radiation is a form of
radiation emitted by bodies
because of their temperature.

Stefan-Boltzmann Law
The rate at which energy is
transferred by thermal radiation
is proportional to the fourth
power of the absolute
temperature of the radiating
body.

P = eAT4 (W)

= 5.67 108
W/m2K4

Example:
A thin square steel plate, 10 cm
on a side is heated in a black
smiths forge to a temperature of
800C. If the emissivity of the
body is 0.6, what is the total rate
of radiation of energy?

Ans: 900 W

Part II
Thermal Properties of
Matter

State Variables
State variables are the quantities
that are used to describe the
state of a system.
State variables depend only of the
initial and final state of the
system.
Examples of state properties are
pressure, volume, temperature
and internal energy.

Equation of State of an Ideal


Gas
constant n and T, P
1/V
At constant n and P, V
T
At constant n and V, P
PV = nRT
T
At constant P and T, V
Rn= 8.314 J/molK
At

R = 0.0821 Latm/
(molK)

Example:
Determine the volume occupied
by one mole of an ideal gas at
STP.

Ans: 22.4 L

Example:
In an automobile engine, a
mixture of air and gasoline is
compressed in the cylinders
before ignited. A typical engine
has a compression ratio of 9:1.
The initial pressure is 27C. If the
pressure after compression is
21.7 atm, find the temperature of
the compressed gas.

Ans: 450C

Kinetic Molecular Theory


The

separation between
individual gas molecules is way
too large compared to their own
individual sizes
The molecules move randomly
obeying Newtons law.
There is no force of attraction or
repulsion between individual
gas molecules.
The collision of molecules to the

Kinetic energy and velocity of


gas molecules
The average translational kinetic
energy of a gas molecule is given
by
3
3
Kav kT
Kt nRT
2
2
The rms speed of a gas molecule
is
3RT
vrms
M

Cp, Cv and R
For monatomic gases , the values
of CV and CP respectively are

3
CV
2

5
CP
2

CP CV R

CP 5 2R 5

1.67
CV
3 2R 3

Part III
The First Law of
Thermodynamics

Thermodynamic System and


Process
A thermodynamic system is any
collection of object that can be
regarded as a unit and has the
potential to exchange energy with
its surroundings
A process that involves a change
in the state of a system is called a
thermodynamic process.

Microscopic and Macroscopic


forms of Energy
The macroscopic forms of energy
are those a system possesses as a
whole with respect to some
outside reference frame.
The microscopic forms of energy
are those related to the molecular
structure of a system.

Introduction to the First law


The first law of thermodynamics
involves systems in which the
only energy change is that of
internal energy, and the only
energy transfer involved is by
means of heat and work.

Internal Energy
The sum of all the microscopic
forms of energy possessed by a
system is called the internal
energy, U.
This energy includes all sort of
kinetic as well as potential energy
of atoms and molecules.

Thermal Energy
Thermal energy maybe defined as
the sum of the kinetic energies of
all the molecules in a system,
including both the sensible and
latent forms of internal energy.

Adiabatic Process
A process that does not involves a
transfer of energy by heat.
In an adiabatic process, the
temperature of the system can
also be changed by other means
such as by doing work.

Energy Transfer by Work


Work is the energy transfer
associated with a force acting to a
system creating a displacement.
The rate at which energy is
transferred is called power. Since
work can be used to transfer
energy, power maybe defined
specifically as the rate of doing

The work done in a quasistatic process


The work done on
or by a gas from
an initial to final
state depends on
the path between
these states.

Vf

w PdV
Vi

w P Vf V

Heat and Work


Both

heat and work are


boundary phenomena
A system may posses energy but
not heat or work.
Both heat and work are
associated with a process, not a
state.
Both heat and work are path
functions.

The First Law of


Thermodynamics
In any process energy can neither
be created nor destroyed; it can
only be converted from one form
to another.
The net change in the total
energy of the system during a
process is equal to the difference
between the total energy entering
and the total energy leaving the
system.

The Energy Balance Equation


The net change in the total
energy of the system during a
process is equal to the difference
between the total energy entering
and the total energy leaving the
system.

E = Ein Eout

The First Law of


Thermodynamics
The energy of a closed system
may only be changed by heat or
work. Thus, the change in the
total energy of the system is
simply equal to the sum of the
energy transferred by heat and
the net work done.

E = Q + W

The First Law of


Thermodynamics
The energy of a closed system
may only be changed by heat or
work. Thus, the change in the
total energy of the system is
simply equal to the sum of the
energy transferred by heat and
the net work done.

E = Q + W

The First Law of


Thermodynamics

E = Q + W
Process
Heat is absorbed by the
system
Heat is gained by the
system
Work is done on the
system

Sign
+

E in a Stationary System
The change in the total energy of
a closed system is equal to the
change in its internal energy.

E = U
U = Q + W

The First Law of


Thermodynamics
The change in the internal energy
of a system is equal to the sum of
the energy transfer by heat and
work.

U = Q + W
Specifically, the first law in this
case is applied to a closed
system.

The First Law of


Thermodynamics

U = Q
W

Being a state function,


+ the change in internal
energy depends only
on the initial and
states of the system.
Process
Sign
Heat absorbed by the
+
system
Heat gained by the

system

State Variables
These are the quantities that are
used to describe the state of a
system.
State variables depend only of the
initial and final state of the
system.
Examples of state properties are
pressure, volume and internal
energy.

Transfer Variables
These are the quantities at the
right side of the conservation of
energy equation.
They are either positive or
negative. Examples are heat and
work.
They are not associated with a
given state of the system but
rather, with a change in the
system.

Cyclic Process
For a cyclic process, the initial
and final states of the system are
identical, and thus, the change in
internal energy must be zero.

U = 0
The internal energy in a cyclic
process remains constant.

Isolated System
In an isolated system, no energy
is transferred between the system
and surroundings either by heat
or by work.

U = 0
The internal energy of an isolated
system remains constant.

E in an Adiabatic Process
In an adiabatic process, no energy
is transferred by heat, thus, the
change in the change in the
energy of the system equal the
net work done.

E = W (adiabatic
process)

Adiabatic Process
TV-1 = constant
PV = constant

Adiabatic Free Expansion


In an adiabatic free expansion,
the change in the internal energy
of the system is zero.

U = 0

Isobaric Process (constant


pressure)
The work done in an isobaric
process is

W = P(Vf Vi)

For expansion, work is


negative
For compression, work is
Q=
mCpT
positive

U = Q + W

Isovolumetric Process
For this process V = 0 and hence
W = 0.

W=0

The heat
transferred is

Q = mCVT
U = Q

Isothermal Process
For an isothermal process
involving an ideal gas, the change
in internal energy is zero.

U = 0
Q = W

Isothermal Expansion
For an isothermal expansion, the
work done is

W = nRT ln
(Vi/Vf)

Example:
A student eats a dinner rated at 2
000 Calories. He wishes to do an
equivalent amount of work in the
gymnasium by lifting a 50.0-kg
barbell. How many times must he
raise the barbell to expend this
much energy? Assume he raises
the barbell 2.00 m each time he
Ans:
8540
lifts it and he regains no energy
times
when
he lowers the barbell.

Example:
A rigid tank contains a hot fluid
that is cooled while being stirred
by a paddle wheel. Initially, the
internal energy of the fluid is 800
kJ. During the cooling process, the
fluid loses 500 kJ of heat, and the
paddle wheel does 100 kJ of work
on the fluid. Determine the final
internal
energy
Ans: 400
kJ of the fluid.
Neglect the energy stored in the

Example:
Suppose 1.00 g of water vaporizes
isobarically at atmospheric
pressure. Its volume in the liquid
state is Vi = Vliquid 1.00 cm3, and
its volume in the vapor state is Vf
= Vvapor = 1 671 cm3. Find the work
done in the expansion and the
change
in internal
energy
Ans: W=
169 J,
U =of the
system.
2.09 kJ

Example:
A 1.0-kg bar of copper is heated
at atmospheric pressure so that
its temperature increases from
20C to 50C. (A) What is the work
done on the copper bar by the
surrounding atmosphere? (B) How
much energy is transferred to the
2
copper
bar
heat?
Ans: W
=by
1.7
(C)
10What
J, is
the increase in internal
energy of
4
Q = 1.2 10 J, U = 1.2
the4copper bar?

Part IV
The Second Law of
Thermodynamics

Reversible and Irreversible


Process
A process that proceeds
spontaneously in one direction
but not the other is called an
irreversible process. All processes
that occur in nature are
A
reversible process is an
irreversible.
idealized process in which the
system is always in
thermodynamic equilibrium with
its surroundings. Thus, a

Quasi-equilibrium process
When a process takes place and
yet the system remains very close
to an equilibrium state, which
makes the process nearly
reversible, the process is called
quasi-static or quasi-equilibrium
process.

Heat Engines
Any device that transforms heat
partly into work or mechanical
energy is called a heat engine.
The matter inside the engine is
called the working substance.
The simplest engine to analyze
are those that involve a cyclic
process.

How a Heat Engine Works


The

working
substance
absorbs energy
by heat from a
high temperature
reservoir
Work is done by
the engine
Energy is
expelled by heat

Work done by a heat engine


The net work W done by a heat
engine equals the net energy
transferred by heat.

W = |Qh| |Qc|

Thermal Efficiency of a Heat


Engine
The thermal efficiency of a heat
engine is the ratio of the work
done by the engine during one
cycle to the energy input at higher
temperature.

Qh Qc
Qc
W
E

1
Qh
Qh
Qh

Kelvin-Planck Statement
It is impossible to construct a
heat engine operating in a cycle
that will produce an amount of
work equal to the amount of input
energy by heat.

Heat Pumps and


Refrigerators
A device that transfers energy
from a cold to hot reservoir is
called a heat pump or a
refrigerator.
The transfer of energy from a cold
to hot reservoir can only be
achieved if work is done on the
engine.

Clausius statement
It is impossible
to construct a
machine that can
transfer energy
by heat from a
lower to higher
temperature
without the
input energy by
work.

The Coefficient of
Performance
The COP is a number that
measures the effectiveness of a
heat pump.

COP

COP

Qc
W
Qh
W

cooling mode

heating mode

Carnot Engine
A Carnot engine is a
theoretical engine that
operates in an ideal,
reversible cycle called
Carnot cycle, and is the
most efficient engine
possible.

Sadi
Carnot

Carnots Theorem
No real heat engine operating
between two energy reservoirs
can be more efficient than a
Carnot engine operating between
the same two reservoirs.

Carnot Cycle

Carnot Engine Efficiency


The thermal efficiency of a Carnot
engine is given by the formula

Tc
eC 1
Th

Entropy
Entropy is a state variable which
measures the degree of disorder
in a system.
Entropy statement of the second
law:
The entropy of the Universe
increases for all real processes.

Entropy
The change in entropy during a
process depends only on the
initial and final states, and thus,
independent of the path

dQ
d =
T
S

dQ
S
T
i

Example:
Calculate the change in entropy
when 500 g of ice melts into liquid
water.

Ans:

Entropy Change in a Reversible


and Irreversible Process
The change in entropy in a
reversible process is zero and
greater than zero in an
irreversible process.

S = 0 (reversible
process)

The Entropy of an isolated


system
The total entropy of an isolated
system always increases for an
irreversible process. For a
reversible process, the total
entropy of the isolated system
remains constant.

Entropy Change in a free


expansion
Free expansion is an irreversible
adiabatic expansion.

S =
nRln

Vf
Vi

Example:
Determine the change in entropy
when 2.4 kg of air expands
adiabatically to four times its
initial value.

Ans:

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