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1.1 Thermodynamics is a branch of natural science concerned with heat and its relation to energy
and work. It defines macroscopic variables (such astemperature, internal energy, entropy, and pressure)
that characterize materials and radiation, and explains how they are related and by what laws they
change with time. Thermodynamics describes the average behavior of very large numbers of microscopic
constituents, and its laws can be derived fromstatistical mechanics.
Much of the empirical content of thermodynamics is contained in the four laws. The first law asserts the
existence of a quantity called the internal energy of a system, which is distinguishable from the kinetic
energy of bulk movement of the system and from its potential energy with respect to its surroundings. The
first law distinguishes transfers of energy between closed systems as heat and as work.[3][4][5] The second
law concerns two quantities called temperature and entropy. Entropy expresses the limitations, arising
from what is known as irreversibility, on the amount of thermodynamic work that can be delivered to an
external system by a thermodynamic process.[6] Temperature, whose properties are also partially
described by the zeroth law of thermodynamics, quantifies the direction of energy flow as heat between
two systems in thermal contact and quantifies the common-sense notions of "hot" and "cold".
1.2 In physics, the phrase thermal equilibrium is used sometimes in the common parlance of the ordinary
language of physical discourse, and sometimes as a specialized technical term in thermodynamics.
As common parlance, the phrase refers to steady states of temperature, which may be spatial or
temporal. The meaning varies from occasion to occasion, as with all ordinary language usages.
Thermal equilibrium as a technical term in thermodynamics can also be used in two senses. One sense is
that of thermal equilibrium within a system for itself. The other sense is that of a relation between the
respective physical states of two bodies. Thermal equilibrium in a system for itself means that the
temperature within the system is spatially and temporally uniform. Thermal equilibrium as a relation
between the physical states of two bodies means that there is actual or implied thermal connection
between them, through a path that is permeable only to heat, and that no energy is transferred through
that path. This technical sense is concerned with the theory of the definition of temperature.
1.3 In thermodynamics, the internal energy is the total energy contained by a thermodynamic system.[1] It
is the energy needed to create the system but excludes the energy to displace the system's surroundings,
any energy associated with a move as a whole, or due to external force fields. Internal energy has two
major components, kinetic energy and potential energy. The kinetic energy is due to the motion of the
system's particles (translations, rotations, vibrations), and the potential energy is associated with the
static rest mass energy of the constituents of matter,static electric energy of atoms within molecules
or crystals, and the static energy of chemical bonds. The internal energy of a system can be changed by
heating the system or by doing work on it;[1] the first law of thermodynamics states that the increase in
internal energy is equal to the total heat added and work done by the surroundings. If the system is
isolated from its surroundings, its internal energy cannot change.
For practical considerations in thermodynamics and engineering it is rarely necessary or convenient to
consider all energies belonging to the total intrinsic energy of a sample system, such as the energy given
by the equivalence of mass. Typically, descriptions only include components relevant to the system under
study. Thermodynamics is chiefly concerned only with changes in the internal energy.
The internal energy is a state function of a system, because its value depends only on the current state of
the system and not on the path taken or process undergone to arrive at this state. It is an extensive
quantity. The SI unit of energy is the joule (J). Some authors use a
corresponding intensivethermodynamic property called specific internal energy which is internal energy
per unit of mass (kilogram) of the system in question. The SI unit of specific internal energy is J/kg. If
intensive internal energy is expressed relative to units of amount of substance (mol), then it is referred to
as molar internal energy and the unit is J/mol.
The internal energy (U) is the sum of all forms of energy (Ei) intrinsic to a thermodynamic system:
It is the energy needed to create the system. It may be divided into potential energy (Upot) and kinetic
energy (Ukin) components:
The kinetic energy of a system arises as the sum of the motions of all the system's particles, whether it be
the motion of atoms, molecules, atomic nuclei, electrons, or other particles. The potential energy includes
all energies given by the mass of particles, by the chemical composition, i.e. the chemical energy stored
in chemical bonds having the potential to undergo chemical reactions, the nuclear energy stored by the
configuration of protons, neutrons, and other elementary particles in atomic nuclei, and the physical force
fields within the system, such as due to internal induced electric or magnetic dipole moment, as well as
the energy of deformation of solids (stress-strain).
Internal energy does not include the energy due to motion of a system as a whole. It further excludes any
kinetic or potential energy the body may have because of its location in externalgravitational, electrostatic,
or electomagnetic fields. It does, however, include the contribution to the energy due to the coupling of
the internal degrees of freedom of the object to such the field. In such a case, the field is included in the
thermodynamic description of the object in the form of an additional external parameter.
For practical considerations in thermodynamics or engineering, it is rarely necessary, convenient, nor
even possible, to consider all energies belonging to the total intrinsic energy of a sample system, such as
the energy given by the equivalence of mass. Typically, descriptions only include components relevant to
the system under study. Indeed in most systems under consideration, especially through
thermodynamics, it is impossible to calculate the total internal energy. [2] Therefore, a convenient null
reference point may be chosen for the internal energy.
The internal energy is an extensive property: it depends on the size of the system, or on the amount of
substance it contains.
At any temperature greater than absolute zero, potential energy and kinetic energy are constantly
converted into one another, but the sum remains constant in an isolated system (cf. table). In the classical
picture of thermodynamics, kinetic energy vanishes at zero temperature and the internal energy is purely
potential energy. However, quantum mechanics has demonstrated that even at zero temperature
particles maintain a residual energy of motion, the zero point energy. A system at absolute zero is merely
in its quantum-mechanical ground state, the lowest energy state available. At absolute zero a system has
attained its minimum attainable entropy.
The kinetic energy portion of the internal energy gives rise to the temperature of the system. Statistical
mechanics relates the pseudo-random kinetic energy of individual particles to the mean kinetic energy of
the entire ensemble of particles comprising a system. Furthermore it relates the mean kinetic energy to
the macroscopically observed empirical property that is expressed as temperature of the system. This
energy is often referred to as the thermal energy of a system,[3] relating this energy, like the temperature,
to the human experience of hot and cold.
Statistical mechanics considers any system to be statistically distributed across an ensemble
of N microstates. Each microstate has an energy Ei and is associated with a probability pi. The internal
energy is the mean value of the system's total energy, i.e., the sum of all microstate energies, each
weighted by their probability of occurrence:
There is a fundamental difference between temperature and heat. Heat is the amount of energy in a
system. The SI units for heat are Joules. A Joule is a Newton times a meter. A Newton is a kilogram-
meter per second squared. Heat is transferred through radiation, conduction and convection. The amount
that molecules are vibrating, rotating or moving is a direct function of the heat content. Energy is
transported by conduction as molecules vibrate, rotate and/or collide into each other. Heat is moved
along similar to dominos knocking down their neighbors in a chain reaction. An increase of
electromagnetic radiation into a system causes the molecules to vibrate, rotate and/or move faster. With
convection, higher energy molecules are mixed with lower energy molecules. When higher energy
molecules are mixed with lower energy molecules the molecular motion will come into equilibrium over
time. The faster moving molecules will slow down and the slow moving molecules will speed up.
Temperature is the MEASURE of the AVERAGE molecular motions in a system and simply has units
of (degrees F, degrees C, or K). Notice that one primary difference between heat and temperature is that
heat has units of Joules and temperature has units of (degrees F, degrees C, or K). Another primary
difference is that energy can be transported without the temperature of a substance changing (e.g. latent
heat, ice water remains at the freezing point even as energy is brought into the ice water to melt more
ice). But, as a general statement (ignoring latent heat), as heat energy increases, the temperature will
increase. If molecules increase in vibration, rotation or forward motion and pass that energy to
neighboring molecules, the measured temperature of the system will increase.
3. Thermometric Scales
Over the centuries, countless thermometric scales have been devised for the quantitative measurement
of temperatures ranging between fixed extremes-typically, the freezing and boiling points of water. Many
of these scales have long since been abandoned. The most widespread are described below.
Named after the Swedish scientist Anders Celsius (1701-1744), the scale has become the international
standard. The scale is "centesimal," i.e. divided into 100 equal parts, each called a degree centigrade or
degree Celsius (symbol: ºC). The 0 value is conventionally assigned to the temperature of melting ice and
the 100 value to the temperature of boiling water, both at sea-level atmospheric pressure.
Named after the scientist Daniel Gabriel Fahrenheit (1686-1736). Now used mainly in the United States
and (but no longer officially) the United Kingdom. The scale is divided into 180 equal parts, each called a
degree Fahrenheit (symbol: ºF). The value 32 is assigned to the temperature of ice and the value 212 to
the temperature of boiling water, both at sea-level atmospheric pressure.
Named after the French scientist René-Antoine Ferchault de Réaumur (1683-1757). The scale is divided
into 80 equal parts, each called a degree Réaumur (symbol: ºR). The value 0 is assigned to the
temperature of melting ice and the value 80 to the temperature of boiling water, both at sea-level
atmospheric pressure.
Absolute (Kelvin) thermometric scale
Developed by the British scientist Lord Kelvin (1824-1907), a pioneer in thermodynamics. Zero degrees
Kelvin-also known as "absolute zero"-represents the lowest possible temperature according to
thermodynamic theory. It is equal to -273.16 degrees centigrade.
4. Absolute zero is the lowest temperature possible. More formally, it is the temperature at
which entropy reaches its minimum value. The laws of thermodynamics state that absolute zero cannot
be reached using only thermodynamic means. A system at absolute zero still possesses quantum
mechanical zero-point energy, the energy of its ground state. The kinetic energy of the ground state
cannot be removed. However, in the classical interpretation, it is zero and the thermal energy of matter
vanishes.[citation needed]
The zero point of any thermodynamic temperature scale, such as Kelvin or Rankine scale, is set at
absolute zero. By international agreement, absolute zero is defined as 0K on the Kelvin scale and as
−273.15° on the Celsius scale.[1][2] This equates to −459.67° on the Fahrenheit scale[3] and 0 R on
the Rankine scale.[2] Scientists have achieved temperatures extremely close to absolute zero, where
matter exhibits quantum effects such as superconductivity and superfluidity.
6. The coefficient of volume expansion for different liquids is given in different values. It is
defined as the amount of expansion per unit length of a material due to a degree change in
temperature. The Coefficient of Volume Expansion is also known as expansivity.