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 Kelvin
Fahrenhei
t Rankine
Temperature Conversions

∆TC 10 5
= =
∆TF 0 18 9
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 constant-
volume 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
One kelvin is temperature scale. It
defined as 1/273.16
is
of based on two fixed
the difference between the
temperatures
triple point of namely theabsolute
water and
absolute zero and the triple point
zero.
of water.
Absolute zero: −273.15°C = 0
K
Triple point (H2O): 0.01°C =
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.
 T
ΔLαL o
Δ
β  3α
 ToΔ
ΔVβV
Example:

Jim uses a steel measuring tape

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

Ans: 50.006
m
Thermal Stress

The expansion or contraction of

materials due to temperature
changes may result to thermal
stress σ, which is analogous to
pressure (force per unit area).

σ = Eα∆T
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
17°C, the cylinder just slips in
between the walls. When it warms
to 25°C, calculate the stress in the
Ans: 26.4
cylinder and kN
the force that it
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
1 BTU =
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=
mc∆T
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
mΔT
 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 1°C.
Q
C
ΔT
 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/mol∙K.
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 for water:
Lf = 80
Q= cal/g
mLv 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 200.0°C and then
dropped into a calorimeter
containing 0.400 kg of water
initially at 20.0°C. The final
equilibrium temperature of the
mixed system is 22.4°C. 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/kg∙°C
Ans: 85.5°C
Example:

Determine the total amount of

energy needed to convert 250 g of
ice at a temperature of −10°C to
steam at 120°C.

Ans: 769 kJ
Example:

What mass of steam initially at

130°C is needed to warm 200 g of
water in a 100 g glass container
from 20.0°C to 50.0°C?

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 ΔT
H  kA
dt Δx

H = heat current in watts

Law of Thermal Conduction

dQ  Th  Tc
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 27°C? How much
Ans:
ice 12.7
melts J/s,day?
in one 3.3
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
Newton’s law of cooling.

dQ
H  hAΔT
dt
Example:

Consider a person standing in a

breezy room at 20°C. 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 29°C,
respectively, and the convection
heat transfer
Ans: 168.1 coefficient is 6 W/m 2

· °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 = σeAT4 (W)
σ = 5.67 × 10–8
W/m2∙K4
Example:

A thin square steel plate, 10 cm

on a side is heated in a black
smith’s forge to a temperature of
800°C. 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
 At constant n and T, P 
1/V
 At constant n and P, V 
T
 At constant n and V, P 
T PV = nRT
 At constant P and T, V 
Rn= 8.314 J/mol∙K
R = 0.0821 L∙atm/
(mol∙K)
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 27°C. If the
pressure after compression is
21.7 atm, find the temperature of
the compressed gas.
Ans: 450°C
Kinetic Molecular Theory
 The separation between
individual gas molecules is way
too large compared to their own
individual sizes
 The molecules move randomly
obeying Newton’s 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 5
CV  CP 
2 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 quasi-
static process

The work done on

or by a gas from
an initial to final
state depends on
the path between Vf
w    PdV
these states. 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 Sign
Heat is absorbed by the +
system
Heat is gained by the −
system
Work is done on the +
system
∆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
Being a state function,
∆U = Q + the change in internal
W 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

TVγ-1 = constant

PVγ = 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= mCp∆T
positive

∆U = Q + W
Isovolumetric Process

For this process ∆V = 0 and hence

W = 0.
W=0

The heat
transferred is
Q = mCV∆T

∆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
Ans: 400
internal kJ of the fluid.
energy
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
Ans: W=
change −169 J,
in internal ∆U =of the
energy
system.
2.09 kJ
Example:

A 1.0-kg bar of copper is heated

at atmospheric pressure so that
its temperature increases from
20°C to 50°C. (A) What is the work
done on the copper bar by the
surrounding atmosphere? (B) How
much energy is transferred to the
copper
Ans: W bar
=by heat?
−1.7 ×(C)
10What
−2
J, is
the increase in internal energy of
Q = 1.2 × 10 J, ∆U = 1.2 ×
4
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.
W Qh  Qc Qc
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.
Qc
COP  cooling mode
W

Qh
COP  heating mode
W
 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
Carnot’s 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 f
dQ
d = ΔS  
T T
S 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.

Vf
∆S =
nRln Vi
Example:

Determine the change in entropy

when 2.4 kg of air expands
adiabatically to four times its
initial value.

Ans: