Thermodynamics

Prepared by:

Harold Jan R.Terano, ECE

Thermodynamics
is the science that deals with the relationship

between heat and other forms of energy.The

word thermodynamics comes from two Greek
words,therme and dynamis meaning heat
and power, respectively.

The term thermodynamics was coined by

James Joule in 1849.
In 1824, Nicolas Leonard Sadi Carnot
published Reflections on the Motive Power
of Fire, a discourse on heat, power and
engine efficiency. He is the Father of
Thermodynamics.

Branches of Thermodynamics
1. Classical Thermodynamics is concern with
thermodynamic states and properties (energy, work and
heat) and with the laws of thermodynamics without atomic
interpretation.
2. Statistical Thermodynamics is the classical
thermodynamics with the inclusion of the atomic and
molecular theories and molecular interpretation.
3. Chemical Thermodynamics is concern with the study
of the interrelation of heat with chemical reactions or with
a physical change of state within the confines of the laws of
thermodynamics.

Properties of Substances
1. Intensive Properties are the substances properties that
do not depend on the amount of the substance present.
Examples: stress, pressure, temperature, density,
melting point, boiling point, etc.
2. Extensive Properties are the substances properties
that depend on the amount of the substance present.
Examples: mass, volume, length, energy, etc.

Phases of Substances
1. Solid: In this phase, the substance does not take the shape
or volume of the container.
2. Subcooled liquid: In this phase, the liquid is nonsaturated. Non-saturated means that it is not at its boiling
point.
3. Saturated liquid: In this phase, the liquid can absorb
as much heat as it can without vaporizing.
4. Liquid-vapor mixture: In this phase, the liquid and
vapor co-exist with the same temperature and pressure.

5. Saturated vapor: In this phase, the vapor has absorbed

more heat than necessary to vaporize it.
6. Ideal gas: In this phase, the gas (a highly superheated
vapor) behaves in accordance with the ideal gas law.
7. Real gas: In this phase, the gas does not behave in
accordance with the ideal gas law.
8. Gas mixtures: In this phase, two or more gases mixed
together freely.
9.Vapor/Gas mixtures: In this phase, two or more gases
mixed freely with water vapor.

Temperature
- is defined as the degree of hotness or coldness of a
substance.This thermodynamic property is dependent on
the substances energy content. Absolute zero is the
temperature at which substances possess no thermal energy.
Absolute temperature is the temperature measures from
absolute zero.

Temperature Scales
1. Fahrenheit Scale named after the German physicist Gabriel Daniel
Fahrenheit.The freezing point is 320F and the boiling point is 2120F of
water.
2. Centigrade or Celsius Scale named after the Swedish astronomer
Anders Celsius.The freezing point is 00C and the boiling point is 1000C of
water.
3. Kelvin Scale named after the British mathematician and physicist
Lord Kelvin (William Thomson Kelvin). He introduced the concept of
absolute zero at 0K, the lowest possible temperature and that is the zero of his
scale.
4. Rankine Scale named after the British engineer and physicist
William J. M. Rankine. He places the absolute zero at 00R.

Thermal Expansion
Linear Expansion: Temperature affects some properties of matter.
A change in temperature causes most solids to change in length by
an amount proportional to their original lengths as well as the
change in its temperature. Mathematically,

Temperature Scale Conversion

Coefficient of Linear Expansion of some materials

Material
Aluminum
Brass
Copper
Concrete
Iron
Lead
Quartz
Silver
Glass
Steel

Coefficient, (x10-5/0C
2.4
2.0
1.7
0.7 1.2
1.2
3
0.05
2
0.4 0.9
1.2

Example 1:
An aluminum rod is 3 m long at 200C is
heated at a temperature of 1000C.
How much elongation would the
aluminum rod obtain?

Answer: 5.76 mm

Area Expansion: The increase of temperature results also for a

change in the surface area of a material. Mathematically,

Volume Expansion: Increase of temperature results to an

expansion in the volume for both solid and liquid materials. Same
for linear expansion, the change in volume is given by,

Example 1:
How much increase in the volume of 50
mL mercury if it is to be heated from
25OC to 100OC?

Answer: 0.675 mL

Heat
-is the energy transferred that takes place from one body to
another due to the temperature difference between them.
The calorie (cal) is defined as the amount of heat required to
raise the temperature of 1 gram of water through a temperature
change of 10C.
The British Thermal Unit (BTU) is defined as the amount of
heat required to raise the temperature of 1 lb of water through a
temperature change of 10F.

Quantity of Heat

Example 1:
What is the temperature in 0C of 2 kg of
glass at 300C after 500 cal of heat have
been added? The specific heat capacity
of glass is 0.2 kcal/kg0C.

Answer: 31.250C

Example 2:
A 0.3 kg copper block at 500C is dropped into
a container of water with a mass of 2 kg at
300C and comes to thermal equilibrium.
What is the final temperature of the water
and steel?

Answer: 30.280C

Latent heat, is the quantity of heat absorbed or released by a

substance undergoing a change of phase. A transition from one
phase to another is called phase change or phase
transition. Such example is the changing of ice to water and
water to steam at constant temperature and pressure. Latent heat is
also called as heat of transformation.
For boiling or evaporation, a phase transition occurs from
liquid phase to gaseous phase.The heat required for this transition
is called as the latent heat of vaporization (Lv). Also, phase
transition from solid to liquid is called latent heat of fusion
(Lf) and transition from solid to gas without becoming liquid is
called latent heat of sublimation (Ls).

Latent Heat

The positive or plus (+) sign indicates heat entering and is used
when the material melts and the negative or minus () sign
indicates heat leaving and is used when the material freezes.
Latent Heats of water at standard atmospheric pressure

Sensible Heat
-is the quantity of heat that changes the temperature of a
substance without change in its phase.
The total heat, QT entering a substance is the sum of the latent
heat and the sensible heat.

Example 1:
How much heat must be absorbed by an
ice of mass 720 g at -100C to take it to
liquid at 150C?

Answer: 71.78 kcal

Heat Transfer
Heat flows from a hotter to a colder body.Transmission of heat or
the movement of heat from the hotter to a colder body can be done
in any of the following ways:
Conduction is a process of heat transfer that occurs only between
regions that are at different temperature and the direction of heat
flow is always from higher to lower temperature.
The heat current is the rate of heat flow, H.

Thermal conductivities of some substances

Example 1:
A concrete wall of a house has a total
area of 50 m2 and thickness of 0.15 m.
The inside temperature is 170C.What is
the rate of heat flow into the house if
the temperature of the outside is 300C?

Answer: 3.47 kW

Example 2:
A copper rod 15 cm long is welded end to end to an
aluminum rod 25 cm long. Both the rods are
insulated on their sides and each rod has a
diameter of 1.5 cm.The other end of the copper rod
is in contact with steam at 1000C and the other
end of the aluminum rod is in contact with water
at 00C. Find the temperature at the junction of the
two bars and the total rate of heat flow.

Answer: 75.790C ; 1,098 W

Convection is the transfer of heat that occurs when the heated substance
itself moves.When the layer of water along the bottom of a pot becomes hot
from a stove, this layer of water expands and these hotter molecules rise
letting the cooler water above them move downward to be heated. Convection
occurs in all heated fluids (liquids and gases) creating convection currents.

Example 1:
Water flows over a plane surface 2 m x 2 m
with a temperature of 600C.The temperature
of the surface is 200C.What is the rate of
heat transfer when the convective heat
transfer coefficient is 2,500 W/m20C?

Answer: 400 kW

Radiation is the only type of heat transfer that can occur in

empty space such as outer space.This requires no material medium
for transmission. Any energy transferred by this method is called
radiant energy.
Stefan-Boltzmann law, states that, The rate at which an object
radiates energy is proportional to the fourth power of its
absolute temperature.

Example 1:
A thin 15 cm x 15 cm steel plate is being
heated to a temperature of 6400C. If the
emissivity is 0.60, what is the total rate
of radiation of energy?

Answer: 1.065 kW

Radiation and Absorption

For a body that is radiating at temperature T, the
surrounding at temperature Ts is also radiating and the
body absorbs some of this radiation from the surrounding.
The net rate of radiation from a body at temperature T
with the surrounding at temperature Ts is given by,

Example 1:
Considering that the total surface area of a
human body is 1.50 m2 and body temperature
is 370C.What is the net rate of radiation from
the body if the surrounding temperature is
250C? The emissivity of a human body is
approximately unity.

Answer: 115 W

Work in Thermodynamic Processes

Work is the product of the displacement of the body
and the force applied in the direction of the
displacement.

Example 1:
100 mL of water is boiled at a constant
pressure of 1 atm becomes 230 mL of
steam.What is the work done by the water
when it vaporizes?

Answer: 13.17 J

Internal Energy
Internal energy is the sum of the energies of
the entire particles in the system and all the
potential energies of interaction between these
particles.

The First Law of Thermodynamics states

that, The change in the internal energy
of a closed thermodynamic system is equal
to the sum of the amount of heat energy
supplied to the system and the work done
on the system.

Example 1:
What is the change in the internal energy of
a system if 5,000 J of heat is added to the
system and 2,300 J of work is done on the
system?

Answer: 7,300 J

Example 2:
150 BTU of heat leaves the system while 100
BTU of work is done on the system, what is
the change in the internal energy of the
system?

Answer: -50 BTU

Entropy and Enthalpy

Entropy is the measure of the unavailability of a
systems energy to do work. It is a measure of the
randomness of molecules in a system.
Natural mechanical process such as friction increases
the entropy of the system. As heat is added, entropy
continually increases and decreases when heat is
removed.

Example 1:
What is the enthalpy of a system if the
internal energy is 300 J and a volume of
0.05 m3 at atmospheric pressure?

Answer: 5.37 kJ

Ideal Gas
The ideal gas laws are:
I. Charles Law (Formulated by the French
physicist, Jacques Charles)
At constant pressure, the volume of gas is directly
proportional to the absolute temperature.

Example 1:
During the daytime, a balloon has a volume
of 2,000mL when the temperature is 320C.
If the temperature dropped to 200C at
night time, what will be the volume of the
balloon if the pressure remains the same?

Answer: 1,921.35 mL

II. Boyles Law (Formulated by an Irish chemist,

Robert Boyle)
At constant temperature, the volume of gas is
inversely proportional to the pressure.

Example 1:
A 100 L of helium gas at room temperature
with a pressure of 2 atm is transferred to
another tank with a maximum capacity of
only 50 L. If temperature is kept constant,
what will be the pressure of the tank after
the transfer?
Answer: 4 atm

III. Gay-Lussacs Law (Formulated by the French

scientist, Joseph Louis Gay-Lussac)
At constant volume, the pressure of gas is directly
proportional to the absolute temperature.

Example 1:
A certain gas has a pressure of 2,500 mmHg
inside a tank is cooled from 3900F to 700R.
What will be the resulting pressure in the
tank?

Answer: 1,558.46 mmHg

IV. Combined Gas Law

This law is the combination of the gas laws.

Example 1:
The tire of a bike has a volume of 0.6m3 and a
pressure of 760 mmHg at 250C. If the bike is
used in the mountain where the pressure is 720
mmHg and the temperature is 200C, what will
be the volume of the tire?

Answer: 0.62 m3

Ideal Gas Equation

The ideal gas equation is given by

Example 1:
At standard temperature and pressure (STP)
for a gas, it is defined to be at a
temperature of 00C and a pressure of 1 atm.
How big is a container to contain a mole of
an ideal gas at STP?

Answer: 22.4 L

Example 2:
What is the pressure of a 100 g oxygen gas if
it is to be contained in a 3 liters tank at a
temperature of 500C?

Answer: 27.62 atm

Specific Heats of an Ideal Gas

Internal Energy of an Ideal Gas

According to Joules Law , the change of
internal energy of an ideal gas is a function
of only the temperature change. Thus, the
change in internal energy, U is,

Enthalpy of an Ideal Gas

The change of enthalpy of an ideal gas is given
by,
Entropy
The change of entropy of a substance receiving
(or delivering) heat is given by,

Heat Engine
Heat engine or Thermal engine is any device
that transforms and converts heat partially into
mechanical energy or work. It is a closed system that
exchanges only heat and work with its surrounding
and that operates in cycles.

Thermal efficiency of any engine or Engine

efficiency denoted by is defined as the quotient

Example 1:
An engine performs 5,200 J of mechanical
work and discards 7,400 J of heat per cycle.
How much heat must be supplied to the
engine in each cycle? What is the thermal
efficiency of the engine?

Answer: 12,600 J, 41.27%

The Carnot Cycle

Carnot engine is an idealized engine that has the
maximum possible efficiency. It is not subject to any
practical difficulties such as friction or heat loss by
conduction or radiation but that obeys all physical laws.
This hypothetical, idealized heat engine was developed by
the French engineer Sadi Carnot (1796-1832) and was
considered to be the Father of Thermodynamics.
The cycle of this engine is called the Carnot cycle, the
most possible efficient cycle.

The heat transfer in a Carnot engine is,

The thermal efficiency of the Carnot engine is,

Example 1:
A Carnot engine takes 3,000 J of heat from a
reservoir at 3000C and discards some heat to
another reservoir at 800C. How much work
does it do? How much heat is discarded and
what is its thermal efficiency?
Answer: 1,151.53 J
1,848.47 J
38.38%

Heat Pump
A heat pump is refrigeration systems that can take heat
from the cold outdoors in winter and deliver it to the
interior of a house.
A refrigerator is a heat engine operating in reverse. A
heat engine takes heat from a hot place and gives off heat
to a colder place. A refrigerator does the reverse; it takes
heat from a cold place (inside the refrigerator) and gives it
off to a warmer place (usually the air outside the
refrigerator).

A coefficient of performance (COP) is the ratio

between the absorbed heat and the work required.
COP is given by,

Energy Efficiency Ratio (EER) of a refrigerator or

air-conditioner is the ratio between the heat in BTU
extracted per hour and the power in units the machine
consumes.

Example 1:
A refrigerator has a coefficient of performance of
2.4. In each cycle it absorbs 45 kJ of heat from
the cold reservoir. How much mechanical energy
is required each cycle to operate the
refrigerator? How much heat is discarded to the
high temperature reservoir?

Answer: 18.75 kJ
63.75 kJ

Laws of Thermodynamics
Zeroth Law
If two thermodynamic systems are separately
in thermal equilibrium with a third, they are
also in thermal equilibrium with each other.
The term zeroth law was coined by Ralph H. Fowler
in the 1920s.

First Law
The change in the internal energy of a closed
thermodynamic system is equal to the sum of
the amount of heat energy supplied to the
system and the work done on the system.
The first law is about the conservation of energy.This was
given by Rudolf Clausius in 1850.

Second Law
First Formulation: Entropy
The total entropy of any isolated
thermodynamic system tends to increase over
time, approaching a maximum value.
Second Formulation: Heat Formulation or Clausius
Statement, formulated by Rudolf Clausius
Heat generally cannot flow spontaneously
from a material at lower temperature to a
material at higher temperature.

Second Law
Third Formulation: Heat Engine Formulation or KelvinPlank Statement, formulated by Lord Kelvin
It is impossible to convert heat
completely into work in a cyclic process.
Fourth Formulation: Caratheodory Statement, formulated
by the Greek mathematician Constantin Caratheodory
In the neighborhood of any equilibrium
state of a thermodynamic system, there are
equilibrium states that are adiabatically
inaccessible.

Third Law

The entropy of all systems and of all

states of a system is zero at absolute
zero.
This was developed by Walther Nernst during the
years 1906-1912 and is sometimes referred to as
Nernsts theorem or Nernsts postulate.

An alternative version of the third law as stated by

Gilbert N. Lewis and Merle Randall in 1923.
If the entropy of each element in some (perfect)
crystalline state be taken as zero at the absolute
zero temperature, every substance has a finite
positive entropy ; but at the absolute zero of
temperature, the entropy may become zero, and
does so become in the case of perfect crystalline
substances.

Fourth Law

Onsager reciprocal relation expresses the

equality of certain relations between
flows and forces in thermodynamic
systems out of equilibrium but where a
notion of local equilibrium exists.