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General Engineering

and Applied Sciences

Thermodynamics

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

Thermodynamics

therme dynamis
heat power
Divisions of Thermodynamics

Thermodynamics

classical statistical
macroscopic microscopic
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 properties.
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
Fahrenheit Rankine
Temperature Conversions

TC 100 5
= =
TF 180 9

9
TF = TC + 32
5

5
TC = (TF 32)
9
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

Absolute
zero!
The Kelvin Scale

The Kelvin scale is considered as the


absolute
One temperature
kelvin scale.
is defined as It is based
1/273.16 of theon
two fixed temperatures
difference namely
between the triple the of
point
absolute
water andzero and the
absolute triple point of
zero.
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
= To
= 3
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 the force
that it exerts on each wall, Assuming that
Ans:
the 26.4
walls arekNperfectly rigid.
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 = 1055 J
BTU
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 for water:


Lf = 80 cal/g
Q = mLv
Lv = 540 cal/g
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:

conduction
convection
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 (W)


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 27C? How much ice melts in one day?

Ans: 12.7 J/s, 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 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 heat transfer coefficient is 6
W/m2 C

Ans: 168.1 W
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

At constant n and T, P 1/V


At constant n and P, V T
At constant n and V, P T
At constant P and T, V n

PV = nRT

R = 8.314 J/molK
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 wall of
the container is a perfect collision.
Kinetic energy and velocity of gas
molecules
The average translational kinetic energy
of a gas molecule is given by
3 3
K av = kT K t = nRT
2 2
The rms speed of a gas molecule is

3RT
v rms =
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 2 R 5
g = = = = 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 work.
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 these states. Vf
w = - PdV
Vi

(
w = -P Vf - Vi )
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 +
Work is done by 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, the


U = Q + W 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
Work done on the system +
Work done 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 positive

Q = mCpT

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 lifts it and he
regains no energy when he lowers the
Ans: 8540 times
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 of the fluid. Neglect the
Ans: 400
energy kJ in the paddle wheel.
stored
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 of the system.

Ans: W= 169 J, U = 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
copper bar by heat? (C) What is the
increase in internal energy of the copper
Ans:
bar? W = 1.7 10 2
J,
Q = 1.2 104 J, U = 1.2 104 J
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 irreversible.

A reversible process is an idealized


process in which the system is always in
thermodynamic equilibrium with its
surroundings. Thus, a reversible process
is an equilibrium process.
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 to a lower
temperature reservoir
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
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 f
dQ
dS = S =
T
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.

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: