LAWS OF THERMODYNAMICS

The laws of thermodynamics are a set of scientific laws which define a group of physical

quantities, such as temperature, energy, and entropy, that characterize thermodynamic
systems in thermodynamic equilibrium. The laws also use various parameters
for thermodynamic processes, such as thermodynamic work and heat, and establish
relationships between them. They state empirical facts that form a basis of precluding the
possibility of certain phenomena, such as perpetual motion. In addition to their use
in thermodynamics, they are important fundamental laws of physics in general, and are
applicable in other natural sciences.

Traditionally, thermodynamics has recognized three fundamental laws, simply named by an

ordinal identification, the first law, the second law, and the third law.[1][2][3] A more
fundamental statement was later labelled as the zeroth law, after the first three laws had been
established.

The zeroth law of thermodynamics defines thermal equilibrium and forms a basis for the

definition of temperature: If two systems are each in thermal equilibrium with a third system,
then they are in thermal equilibrium with each other.

The first law of thermodynamics states that, when energy passes into or out of a system
(as work, heat, or matter), the system's internal energy changes in accordance with the law
of conservation of energy.

The second law of thermodynamics states that in a natural thermodynamic process, the sum

of the entropies of the interacting thermodynamic systems never decreases. A common
corollary of the statement is that heat does not spontaneously pass from a colder body to a
warmer body.

The third law of thermodynamics states that a system's entropy approaches a constant value

as the temperature approaches absolute zero. With the exception of non-crystalline solids
(glasses), the entropy of a system at absolute zero is typically close to zero.[2]

The first and second laws prohibit two kinds of perpetual motion machines, respectively:
the perpetual motion machine of the first kind which produces work with no energy input,
and the perpetual motion machine of the second kind which spontaneously converts thermal
energy into mechanical work.

History
The history of thermodynamics is fundamentally interwoven with the history of physics and
the history of chemistry, and ultimately dates back to theories of heat in antiquity. The laws
of thermodynamics are the result of progress made in this field over the nineteenth and early
twentieth centuries. The first established thermodynamic principle, which eventually became
the second law of thermodynamics, was formulated by Sadi Carnot in 1824 in his
book Reflections on the Motive Power of Fire. By 1860, as formalized in the works of
scientists such as Rudolf Clausius and William Thomson, what are now known as the first
and second laws were established. Later, Nernst's theorem (or Nernst's postulate), which is
now known as the third law, was formulated by Walther Nernst over the period 1906–1912.
While the numbering of the laws is universal today, various textbooks throughout the 20th
century have numbered the laws differently. In some fields, the second law was considered to
deal with the efficiency of heat engines only, whereas what was called the third law dealt
with entropy increases. Gradually, this resolved itself and a zeroth law was later added to
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allow for a self-consistent definition of temperature. Additional laws have been suggested,
but have not achieved the generality of the four accepted laws, and are generally not
discussed in standard textbooks.

Zeroth law
The zeroth law of thermodynamics provides for the foundation of temperature as an empirical
parameter in thermodynamic systems and establishes the transitive relation between the
temperatures of multiple bodies in thermal equilibrium. The law may be stated in the
following form:
If two systems are both in thermal equilibrium with a third system, then they are in thermal
equilibrium with each other.[4]

Though this version of the law is one of the most commonly stated versions, it is only one of
a diversity of statements that are labeled as "the zeroth law". Some statements go further, so
as to supply the important physical fact that temperature is one-dimensional and that one can
conceptually arrange bodies in a real number sequence from colder to hotter.[5][6][7]

These concepts of temperature and of thermal equilibrium are fundamental to

thermodynamics and were clearly stated in the nineteenth century. The name 'zeroth law' was
invented by Ralph H. Fowler in the 1930s, long after the first, second, and third laws were
widely recognized. The law allows the definition of temperature in a non-circular way
without reference to entropy, its conjugate variable. Such a temperature definition is said to
be 'empirical'.[8][9][10][11][12][13]

First law
The first law of thermodynamics is a version of the law of conservation of energy, adapted
for thermodynamic processes. In general, the conservation law states that the total energy of
an isolated system is constant; energy can be transformed from one form to another, but can
be neither created nor destroyed.
In a closed system (i.e. there is no transfer of matter into or out of the system), the first law
states that the change in internal energy of the system (ΔUsystem) is equal to the difference
between the heat supplied to the system (Q) and the work (W) done by the system on its
surroundings. (Note, an alternate sign convention, not used in this article, is to define W as
the work done on the system by its surroundings):

For processes that include transfer of matter, a further statement is needed.

When two initially isolated systems are combined into a new system, then the total internal
energy of the new system, Usystem, will be equal to the sum of the internal energies of the two
initial systems, U1 and U2:

The First Law encompasses several principles:

Conservation of energy, which says that energy can be neither created nor destroyed, but can
only change form. A particular consequence of this is that the total energy of an isolated
system does not change.
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The concept of internal energy and its relationship to temperature. If a system has a definite
temperature, then its total energy has three distinguishable components, termed kinetic
energy (energy due to the motion of the system as a whole), potential energy (energy
resulting from an externally imposed force field), and internal energy. The establishment of
the concept of internal energy distinguishes the first law of thermodynamics from the more
general law of conservation of energy.

Work is a process of transferring energy to or from a system in ways that can be described by
macroscopic mechanical forces acting between the system and its surroundings. The work
done by the system can come from its overall kinetic energy, from its overall potential
energy, or from its internal energy.
For example, when a machine (not a part of the system) lifts a system upwards, some energy
is transferred from the machine to the system. The system's energy increases as work is done
on the system and in this particular case, the energy increase of the system is manifested as an
increase in the system's gravitational potential energy. Work added to the system increases
the potential energy of the system:
When matter is transferred into a system, the internal energy and potential energy associated
with it are transferred into the new combined system.

where u denotes the internal energy per unit mass of the transferred matter, as measured
while in the surroundings; and ΔM denotes the amount of transferred mass.
The flow of heat is a form of energy transfer. Heat transfer is the natural process of moving
energy to or from a system other than by work or the transfer of matter. In
a diathermal system, the internal energy can only be changed by the transfer of energy as
heat:

Combining these principles leads to one traditional statement of the first law of
thermodynamics: it is not possible to construct a machine which will perpetually output work
without an equal amount of energy input to that machine. Or more briefly, a perpetual motion
machine of the first kind is impossible.

Second law
The second law of thermodynamics indicates the irreversibility of natural processes, and in
many cases, the tendency of natural processes to lead towards spatial homogeneity of matter
and energy, especially of temperature. It can be formulated in a variety of interesting and
important ways. One of the simplest is the Clausius statement, that heat does not
spontaneously pass from a colder to a hotter body.

It implies the existence of a quantity called the entropy of a thermodynamic system. In terms

of this quantity it implies that
When two initially isolated systems in separate but nearby regions of space, each
in thermodynamic equilibrium with itself but not necessarily with each other, are then
allowed to interact, they will eventually reach a mutual thermodynamic equilibrium. The sum
of the entropies of the initially isolated systems is less than or equal to the total entropy of the
final combination. Equality occurs just when the two original systems have all their

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respective intensive variables (temperature, pressure) equal; then the final system also has the
same values.

The second law is applicable to a wide variety of processes, both reversible and irreversible.
According to the second law, in a reversible heat transfer, an element of heat transferred, 

, is the product of the temperature ( ), both of the system and of the sources or

destination of the heat, with the increment ( ) of the system's conjugate variable,

its entropy ( ):

[1]

While reversible processes are a useful and convenient theoretical limiting case, all natural
processes are irreversible. A prime example of this irreversibility is the transfer of heat by
conduction or radiation. It was known long before the discovery of the notion of entropy that
when two bodies, initially of different temperatures, come into direct thermal connection,
then heat immediately and spontaneously flows from the hotter body to the colder one.

Entropy may also be viewed as a physical measure concerning the microscopic details of the
motion and configuration of a system, when only the macroscopic states are known. Such
details are often referred to as disorder on a microscopic or molecular scale, and less often
as dispersal of energy. For two given macroscopically specified states of a system, there is a
mathematically defined quantity called the 'difference of information entropy between them'.
This defines how much additional microscopic physical information is needed to specify one
of the macroscopically specified states, given the macroscopic specification of the other –
often a conveniently chosen reference state which may be presupposed to exist rather than
explicitly stated. A final condition of a natural process always contains microscopically
specifiable effects which are not fully and exactly predictable from the macroscopic
specification of the initial condition of the process. This is why entropy increases in natural
processes – the increase tells how much extra microscopic information is needed to
distinguish the initial macroscopically specified state from the final macroscopically specified
state.[14] Equivalently, in a thermodynamic process, energy spreads.

Third law
The third law of thermodynamics can be stated as:[2]
A system's entropy approaches a constant value as its temperature approaches absolute zero.

a) Single possible configuration for a system at absolute zero, i.e., only one microstate is
accessible. b) At temperatures greater than absolute zero, multiple microstates are accessible
due to atomic vibration (exaggerated in the figure)

At zero temperature, the system must be in the state with the minimum thermal energy,
the ground state. The constant value (not necessarily zero) of entropy at this point is called

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the residual entropy of the system. Note that, with the exception of non-crystalline solids
(e.g., glasses) the residual entropy of a system is typically close to zero.[2] However, it
reaches zero only when the system has a unique ground state (i.e., the state with the minimum
thermal energy has only one configuration, or microstate). Microstates are used here to
describe the probability of a system being in a specific state, as each microstate is assumed to
have the same probability of occurring, so macroscopic states with fewer microstates are less
probable. In general, entropy is related to the number of possible microstates according to
the Boltzmann principle

where S is the entropy of the system, kB Boltzmann's constant, and Ω the number of

microstates. At absolute zero there is only 1 microstate possible (Ω=1 as all the atoms are
identical for a pure substance, and as a result all orders are identical as there is only one

combination) and  .

Onsager relations
The Onsager reciprocal relations have been considered the fourth law of thermodynamics.[15]
[16][17] They describe the relation between thermodynamic flows and forces in non-

equilibrium thermodynamics, under the assumption that thermodynamic variables can be

defined locally in a condition of local equilibrium. These relations are derived from statistical
mechanics under the principle of microscopic reversibility (in the absence of
external magnetic fields). Given a set of extensive parameters Xi (energy, mass, entropy,
number of particles) and thermodynamic forces Fi (related to intrinsic parameters, such as
temperature and pressure), the Onsager theorem states that[16]

where

are called the thermodynamic flows.

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