Definitions' and

Basic Principles of
Thermodynamics
Thermodynamics
• Thermodynamics is a branch of physics
that deals with heat and temperature, and
their relation to energy, work, radiation,
and properties of matter.
Branches of
Thermodynamics
 • Is the description of the states of thermodynamic
Classical systems at near-equilibrium, that uses
macroscopic, measurable properties. It is used to
thermodynamics model exchanges of energy, work and heat based
on the laws of thermodynamics.
 • Also called statistical thermodynamics, emerged
with the development of atomic and molecular
theories in the late 19th century and early 20th
century, and supplemented classical
thermodynamics with an interpretation of the
microscopic interactions between individual
Statistical particles or quantum-mechanical states.
• This field relates the microscopic properties of
mechanics individual atoms and molecules to the
macroscopic, bulk properties of materials that can
be observed on the human scale, thereby
explaining classical thermodynamics as a natural
result of statistics, classical mechanics, and
quantum theory at the microscopic level.
 • Is the study of the interrelation of energy with
Chemical chemical reactions or with a physical change of
state within the confines of the laws of
Thermodynamics thermodynamics.
Equilibrium
Thermodynamics

• Is the study of transfers of

matter and energy in
systems or bodies that, by
agencies in their
surroundings, can be
driven from one state of
thermodynamic
equilibrium to another.
Working Substance
• In thermodynamics, working substance is the term used by
French physicist Sadi Carnot in 1824 to define any
generalized body, such as a body of water, a metallic bar, an
aeriform fluid, etc., that may be configured to do work when
put in alternating contact with hot and cold bodies able to
supply or absorb heat.
• In 1850, building on the work of Carnot, German physicist
Rudolf Clausius rephrased this concept using the term
"working body" Carnot’s original diagram of this “working
substance” is pictured adjacent with the hot body A, the cold
body B, and the working substance contained within the
cylinder and the adjustable piston.
Types of Thermodynamic Systems
Open
system
• The system in which the transfer of
mass as well as energy can take place
across its boundary is called as an
open system. Our previous example of
engine is an open system. In this case
we provide fuel to engine and it
produces power which is given out,
thus there is exchange of mass as well
as energy. The engine also emits heat
which is exchanged with the
surroundings. The other example of
open system is boiling water in an
open vessel, where transfer of heat as
well as mass in the form of steam
takes place between the vessel and
surrounding.
Closed
System
• The system in which the transfer of
energy takes place across its boundary
with the surrounding, but no transfer
of mass takes place is called as closed
system. The closed system is fixed
mass system. The fluid like air or gas
being compressed in the piston and
cylinder arrangement is an example of
the closed system. In this case the
mass of the gas remains constant but
it can get heated or cooled. Another
example is the water being heated in
the closed vessel, where water will get
heated but its mass will remain same.
Isolated
System
• The system in which neither the
transfer of mass nor that of energy
takes place across its boundary with
the surroundings is called as isolated
system. For example if the piston and
cylinder arrangement in which the
fluid like air or gas is being compressed
or expanded is insulated it becomes
isolated system. Here there will
neither transfer of mass nor that of
energy. Similarly hot water, coffee or
tea kept in the thermos flask is closed
system. However, if we pour this fluid
in a cup, it becomes an open system.
Properties
Intensive
• Intensive is a property which is independent of
the amount of material in the system like
thermal conductivity , temperature, boiling
point, freezing point, surface tension, density ,
viscosity.
• Pressure
• Temperature
• Density
• Concentration
• Meting Point
• Boiling Point
• Surface Tension
• Viscosity
Extensive
• An extensive property of a system depends upon
the total amount of material in the system.
Mass, volume, internal energy, heat contents,
free energy, entropy, and heat capacity are all
extensive properties.
• Mass
• Volume
• Internal Energy
• Heat Capacity
• Enthalpy
• Entropy
• Helmholtz Energy
• Gibbs Energy
Definitions
 • Thermodynamics, then, is concerned with several
properties of matter; foremost among these is
heat. Heat is energy transferred between
substances or systems due to a temperature
difference between them, according to Energy
Education. As a form of energy, heat is conserved,
i.e., it cannot be created or destroyed. It can,
Heat however, be transferred from one place to another.
Heat can also be converted to and from other
forms of energy. For example, a steam turbine can
convert heat to kinetic energy to run a generator
that converts kinetic energy to electrical energy. A
light bulb can convert this electrical energy to
electromagnetic radiation (light), which, when
absorbed by a surface, is converted back into heat.
 • The amount of heat transferred by a substance depends on the speed and
number of atoms or molecules in motion, according to Energy Education.
The faster the atoms or molecules move, the higher the temperature, and
the more atoms or molecules that are in motion, the greater the quantity
of heat they transfer.

• Temperature is "a measure of the average kinetic energy of the particles in

a sample of matter, expressed in terms of units or degrees designated on a
standard scale," according to the American Heritage Dictionary. The most
commonly used temperature scale is Celsius, which is based on the

Temperature freezing and boiling points of water, assigning respective values of 0

degrees C and 100 degrees C. The Fahrenheit scale is also based on the
freezing and boiling points of water which have assigned values of 32 F and
212 F, respectively.

• Scientists worldwide, however, use the Kelvin (K with no degree sign) scale,
named after William Thomson, 1st Baron Kelvin, because it works in
calculations. This scale uses the same increment as the Celsius scale, i.e., a
temperature change of 1 C is equal to 1 K. However, the Kelvin scale starts
at absolute zero, the temperature at which there is a total absence of heat
energy and all molecular motion stops. A temperature of 0 K is equal to
minus 459.67 F or minus 273.15 C.
 • The amount of heat required to increase the temperature
of a certain mass of a substance by a certain amount is
called specific heat, or specific heat capacity, according to
Wolfram Research. The conventional unit for this is calories
per gram per kelvin. The calorie is defined as the amount
of heat energy required to raise the temperature of 1 gram
of water at 4 C by 1 degree.

Specific • The specific heat of a metal depends almost entirely on the

Heat number of atoms in the sample, not its mass. For instance,
a kilogram of aluminum can absorb about seven times
more heat than a kilogram of lead. However, lead atoms
can absorb only about 8 percent more heat than an equal
number of aluminum atoms. A given mass of water,
however, can absorb nearly five times as much heat as an
equal mass of aluminum. The specific heat of a gas is more
complex and depends on whether it is measured at
constant pressure or constant volume.
 • Thermal conductivity (k) is “the rate at which heat passes through
a specified material, expressed as the amount of heat that flows
per unit time through a unit area with a temperature gradient of
one degree per unit distance,” according to the Oxford Dictionary.
The unit for k is watts (W) per meter (m) per kelvin (K). Values of k
for metals such as copper and silver are relatively high at 401 and
428 W/m·K, respectively. This property makes these materials
useful for automobile radiators and cooling fins for computer
chips because they can carry away heat quickly and exchange it
Thermal with the environment. The highest value of k for any natural
substance is diamond at 2,200 W/m·K.

Conductivity • Other materials are useful because they are extremely poor
conductors of heat; this property is referred to as thermal
resistance, or R-value, which describes the rate at which heat is
transmitted through the material. These materials, such as rock
wool, goose down and Styrofoam, are used for insulation in
exterior building walls, winter coats and thermal coffee mugs. R-
value is given in units of square feet times degrees Fahrenheit
times hours per British thermal unit (ft2·°F·h/Btu) for a 1-inch-
thick slab.
Newton's Law of Cooling
• In 1701, Sir Isaac Newton first stated his Law of Cooling in a short article titled
"Scala graduum Caloris" ("A Scale of the Degrees of Heat") in the Philosophical
Transactions of the Royal Society. Newton's statement of the law translates from
the original Latin as, "the excess of the degrees of the heat ... were in geometrical
progression when the times are in an arithmetical progression." Worcester
Polytechnic Institute gives a more modern version of the law as "the rate of
change of temperature is proportional to the difference between the
temperature of the object and that of the surrounding environment."

• This results in an exponential decay in the temperature difference. For example,

if a warm object is placed in a cold bath, within a certain length of time, the
difference in their temperatures will decrease by half. Then in that same length of
time, the remaining difference will again decrease by half. This repeated halving
of the temperature difference will continue at equal time intervals until it
becomes too small to measure.
Heat Transfer
Heat can be transferred from one body to another or between a body and the
environment by three different means: conduction, convection and radiation.
Conduction is the transfer of energy through a solid material. Conduction between
bodies occurs when they are in direct contact, and molecules transfer their energy
across the interface.

Convection is the transfer of heat to or from a fluid medium. Molecules in a gas or

liquid in contact with a solid body transmit or absorb heat to or from that body and
then move away, allowing other molecules to move into place and repeat the
process. Efficiency can be improved by increasing the surface area to be heated or
cooled, as with a radiator, and by forcing the fluid to move over the surface, as with a
fan.
Radiation is the emission of electromagnetic (EM) energy, particularly infrared
photons that carry heat energy. All matter emits and absorbs some EM radiation, the
net amount of which determines whether this causes a loss or gain in heat.
The Carnot Cycle
• In 1824, Nicolas Léonard Sadi Carnot proposed a model for a heat engine based on what has
come to be known as the Carnot cycle. The cycle exploits the relationships among pressure,
volume and temperature of gasses and how an input of energy can change form and do work
outside the system.

• Compressing a gas increases its temperature so it becomes hotter than its environment. Heat can
then be removed from the hot gas using a heat exchanger. Then, allowing it to expand causes it to
cool. This is the basic principle behind heat pumps used for heating, air conditioning and
refrigeration.

• Conversely, heating a gas increases its pressure, causing it to expand. The expansive pressure can
then be used to drive a piston, thus converting heat energy into kinetic energy. This is the basic
principle behind heat engines.
Entropy
• All thermodynamic systems generate waste heat. This waste results in an increase in entropy, which for a closed system is "a
quantitative measure of the amount of thermal energy not available to do work," according to the American Heritage Dictionary.
Entropy in any closed system always increases; it never decreases. Additionally, moving parts produce waste heat due to friction,
and radiative heat inevitably leaks from the system.

• This makes so-called perpetual motion machines impossible. Siabal Mitra, a professor of physics at Missouri State University,
explains, "You cannot build an engine that is 100 percent efficient, which means you cannot build a perpetual motion machine.
However, there are a lot of folks out there who still don't believe it, and there are people who are still trying to build perpetual
motion machines."

• Entropy is also defined as "a measure of the disorder or randomness in a closed system," which also inexorably increases. You can
mix hot and cold water, but because a large cup of warm water is more disordered than two smaller cups containing hot and cold
water, you can never separate it back into hot and cold without adding energy to the system. Put another way, you can’t
unscramble an egg or remove cream from your coffee. While some processes appear to be completely reversible, in practice, none
actually are. Entropy, therefore, provides us with an arrow of time: forward is the direction of increasing entropy.
Laws of Thermodynamics
Zero th Law
• If two systems are each in thermal equilibrium with a third, they are
also in thermal equilibrium with each other.
First Law
• In a process without transfer of matter, the change in internal energy, ΔU, of a
thermodynamic system is equal to the energy gained as heat, Q, less the
thermodynamic work, W, done by the system on its surroundings.
• U= Q - W
• For processes that include transfer of matter, a further statement is needed: With
due account of the respective fiducial reference states of the systems, when two
systems, which may be of different chemical compositions, initially separated only
by an impermeable wall, and otherwise isolated, are combined into a new system
by the thermodynamic operation of removal of the wall, then
• U0 = U1 + U2
• where U0 denotes the internal energy of the combined system, and U1 and U2
denote the internal energies of the respective separated systems.
Second Law
• Heat cannot spontaneously flow from
a colder location to a hotter location.
• The total entropy of an isolated
system can never decrease over time,
and is constant if and only if all
processes are reversible. Isolated
systems spontaneously evolve towards
thermodynamic equilibrium, the state
with maximum entropy.
Third Law
• As the temperature of a system approaches absolute zero, all
processes cease and the entropy of the system approaches a
minimum value.