The laws of thermodynamics, in principle, describe the specifics for

the transport of heat and work in thermodynamic processes. Since

their inception, however, these laws have become some of the most
important in all of physics and other types of science associated with
thermodynamics.

It is wise to distinguish classical thermodynamics, which is focused on

systems in thermodynamic equilibrium, from non-equilibrium
thermodynamics. The present article is focused on classical or
thermodynamic equilibrium thermodynamics.

There are generally considered to be four principles (referred to as

"laws"):

1. The zeroth law of thermodynamics, which underlies the definition of temperature.

2. The first law of thermodynamics, which mandates conservation of energy, and
states in particular that heat is a form of energy.
3. The second law of thermodynamics, which states that the entropy of an isolated
macroscopic system never decreases, or (equivalently) that perpetual motion
machines are impossible.
4. The third law of thermodynamics, which concerns the entropy of a perfect crystal
at absolute zero temperature, and implies that it is impossible to cool a system all
the way to exactly absolute zero.

During the last 80 years or so, occasionally, various writers have

suggested additional Laws, but none of them have become well
accepted.
Contents
[hide]
 1 Zeroth law
 2 First law
o 2.1 Fundamental Thermodynamic Relation
 3 Second law
 4 Third law
 5 Tentative fourth laws or principles
 6 History
 7 See also
 8 References

 9 Further reading

[edit] Zeroth law

Main article: Zeroth law of thermodynamics
 If two thermodynamic systems are each in thermal
equilibrium with a third, then they are in thermal
equilibrium with each other.

When two systems are put in contact with each other, there will be a
net exchange of energy between them unless or until they are in
thermal equilibrium, that is, they are at the same temperature. While
this is a fundamental concept of thermodynamics, the need to state it
explicitly was not perceived until the first third of the 20th century,
long after the first three principles were already widely in use, hence
the zero numbering. The Zeroth Law asserts that thermal equilibrium,
viewed as a binary relation, is a transitive relation (and since any
system is always in equilibrium with itself, it is furthermore an
equivalence relation).

[edit] First law

Main article: First law of thermodynamics
Energy can neither be created nor destroyed. It can only
change forms.

In any process in an isolated system, the total energy

remains the same.

For a thermodynamic cycle the net heat supplied to the

system equals the net work done by the system.

The First Law states that energy cannot be created or destroyed;

rather, the amount of energy lost in a steady state process cannot be
greater than the amount of energy gained. This is the statement of
conservation of energy for a thermodynamic system. It refers to the
two ways that a closed system transfers energy to and from its
surroundings – by the process of heating (or cooling) and the process
of mechanical work. The rate of gain or loss in the stored energy of a
system is determined by the rates of these two processes. In open
systems, the flow of matter is another energy transfer mechanism, and
extra terms must be included in the expression of the first law.
The First Law clarifies the nature of energy. It is a stored quantity which
is independent of any particular process path, i.e., it is independent of
the system history. If a system undergoes a thermodynamic cycle,
whether it becomes warmer, cooler, larger, or smaller, then it will have
the same amount of energy each time it returns to a particular state.
Mathematically speaking, energy is a state function and infinitesimal
changes in the energy are exact differentials.
All laws of thermodynamics but the First are statistical and simply
describe the tendencies of macroscopic systems. For microscopic
systems with few particles, the variations in the parameters become
larger than the parameters themselves, and the assumptions of
thermodynamics become meaningless. The First Law, i.e. the law of
conservation, has become the most secure of all basic principles of
science. At present, it is unquestioned (although it is said to be
criticized by people who do not accept the idea that the potential to
gain energy is a form of actual energy).

[edit] Fundamental Thermodynamic Relation

The first law can be expressed as the Fundamental Thermodynamic

Relation:
Heat supplied = internal energy + work done

Internal energy = Heat supplied - work done

Here, E is internal energy, T is temperature, S is entropy, p is pressure,
and V is volume. This is a statement of conservation of energy: The net
change in internal energy (dE) equals the heat energy that flows in
(TdS), minus the energy that flows out via the system performing work
(pdV).

[edit] Second law

Main article: Second law of thermodynamics
The entropy of an isolated system consisting of two regions
of space, isolated from one another, each in
thermodynamic equilibrium in itself, but not in equilibrium
with each other, will, when the isolation that separates the
two regions is broken, so that the two regions become able
to exchange matter or energy, tend to increase over time,
approaching a maximum value when the jointly
communicating system reaches thermodynamic
equilibrium.

In a simple manner, the second law states "energy systems have a

tendency to increase their entropy rather than decrease it." This can
also be stated as "heat can spontaneously flow from a higher-
temperature region to a lower-temperature region, but not the other
way around." (Heat can flow from cold to hot, but not spontaneously—-
for example, when a refrigerator expends electrical power.)
A way of thinking about the second law for non-scientists is to consider
entropy as a measure of ignorance of the microscopic details of the
system. So, for example, one has less knowledge about the separate
fragments of a broken cup than about an intact one, because when the
fragments are separated, one does not know exactly whether they will
fit together again, or whether perhaps there is a missing shard. Solid
crystals, the most regularly structured form of matter, have very low
entropy values; and gases, which are very disorganized, have high
entropy values. This is because the positions of the crystal atoms are
more predictable than are those of the gas atoms.
The entropy of an isolated macroscopic system never decreases.
However, a microscopic system may exhibit fluctuations of entropy
opposite to that stated by the Second Law (see Maxwell's demon and
Fluctuation Theorem).

[edit] Third law

Main article: Third law of thermodynamics
As temperature approaches absolute zero, the entropy of a
system approaches a constant minimum.

Briefly, this postulates that entropy is temperature dependent and

results in the formulation of the idea of absolute zero.

[edit] Tentative fourth laws or principles

Over the years, various thermodynamic researchers have come
forward to ascribe to or to postulate potential fourth laws of
thermodynamics (either suggesting that a widely-accepted principle
should be called the fourth law, or proposing entirely new laws); in
some cases, even fifth or sixth laws of thermodynamics are proposed [1].
Most fourth law statements, however, are speculative and
controversial.
The most commonly proposed Fourth Law is the Onsager reciprocal
relations, which give a quantitative relation between the parameters of
a system in which heat and matter are simultaneously flowing.
Other tentative fourth law statements are attempts to apply
thermodynamics to evolution. During the late 19th century,
thermodynamicist Ludwig Boltzmann argued that the fundamental
object of contention in the life-struggle in the evolution of the organic
world is 'available energy'. Another example is the maximum power
principle as put forward initially by biologist Alfred Lotka in his 1922
article Contributions to the Energetics of Evolution.[2] Most variations of
hypothetical fourth laws (or principles) have to do with the
environmental sciences, biological evolution, or galactic phenomena.[3]
 The field of thermodynamics studies the behavior
of energy flow in natural systems. From this
study, a number of physical laws have been
established. The laws of thermodynamics
describe some of the fundamental truths of
thermodynamics observed in our Universe.
Understanding these laws is important to students
of Physical Geography because many of the
processes studied involve the flow of energy.

Zeroth Law First Law Second Law Third Law

When each of two Because energy cannot be Entropy—that is, the The Third Law of
systems is in created or destroyed (with the disorder—of an isolated thermodynamics states
equilibrium with a special exception of nuclear system can never decrease. that absolute zero
third, the first two reactions) the amount of heat Therefore, when an isolated cannot be attained by
systems must be in transferred into a system plus system achieves a any procedure in a finite
equilibrium with each the amount of work done on configuration of maximum number of steps.
other. This shared the system must result in a entropy, it can no longer Absolute zero can be
property of corresponding increase of undergo change (it has approached arbitrarily
equilibrium is the internal energy in the system. reached equilibrium). closely, but it can never
temperature. The Heat and work are mechanisms Additionally, it is not be reached
concept of by which systems exchange enough to conserve energy
temperature is based energy with one another. This and thus obey the First
on this Zeroth Law. First Law of thermodynamics Law. A machine that would
identifies caloric, or heat, as a deliver work while violating
form of energy. the second law is called a
"perpetual-motion machine
of the second kind." In such
a system, energy could then
be continually drawn from a
cold environment to do
work in a hot environment
at no cost.

These are Natural Laws, i.e. they are fundamental and can not be negotiated. On
the other hand, if somebody find out something that might falsify them, they will
cease to be fundamental.

The First Law tells us that energy can be neither created nor
destoyed.
(The production or consumption of energy is impossible. Anyone
who speaks about 'energy production', or 'energy consumption' is
probably ignorant about the First Law). This means that the amount
of energy in the universe is constant.
So, the First Law tells us something about the state of the
universe and all processes in it.

The Second Law tells us that the quality of a particular amount of

energy i.e. the amount of work, or action, that it can do, diminishes
for each time this energy is used. This is true for all instances of
energy use, physical, metbolic, interactive, and so on.
This means that the quality of energy in the universe as a whole, is
constantly diminishing. All real processes are irreversible, since the
quality of the energy driving them is lowered for all times.
Thus, the Second Law tells us about the direction of the universe
and all processes, namely towards a decreasing exergy content of
the universe. Processes that follows this general principle will be
preferred.
Some people seem to think that this law should be revoked... But
perhaps they are misled by their notion of entropy.
The usable energy in a system is called exergy, and can be
measured as the total of the free energies in the system.
Unlike energy, exergy can be consumed.

To more easily understand the concept of exergy, you can consider

this picture as an analogy: You buy is the (toothpaste) tube. But you
have to squeeze it to get at what you really need, the toothpaste.
When the tube is empty of paste (exergy) the tube is still there, the
same amount as when you bought it.
In theese circumstances, the word entropy often comes up. In the
picture this is represented as the depression in the tube. The
depression increases as the amount of paste diminishes, but the
depression is not a negative paste. (You can not take the
depression and unbrush your teeth!)
Entropy is not negative exergy, but another description of the
system. Furthermore, it is not defined in far-from-equilibrium
systems, as living systems and other organised systems.

Life-processes consume the exergy in the energy. After the energy

is used, it contains a lower amount of exergy. The extracted energy
is low-exergy energy, not entropy.
Exergy consumption by living systems

Life-processes are more efficient in consuming exergy than non-

living processes. Therefore, when living systems appears, they offer
a faster route of exergy consumption, and hence a better way of
'obeying' the Second Law.