the laws of thermodynamics, are highly condensed expressions of a broad body of

experimental evidence. The formulation of these succint empirical statements about

the behaviour of matter was essentially completed b the end of 19th century and has
not required significant alteration in the light os scientific experience since
that time.
the laws are empirical: derived from experimental observation of how matter
behaves. No claim is made that they may be deduced from any fundamental
philosophical principles.
the laws of thermodynamics have a status in science that is similar to newton's
laws of motion in mechanics and are similarly subject to potential revision in the
light of new information.
when it was found in physics that new evidence could only be explained by modifying
newton's laws with Einstein's relativistic concepts, the laws of motion were
generalized.
however, this generalization was in such a form that the new equations simplify to
newton's laws when the velocity of the system is not a significant fraction of the
velocity of light.
newton's laws were not abandoned; they were expanded to include newly discovered
phenomena. classical mechanics could be viewed as a special case of the new
relativistic mechanics. This strategy was necessary because classical mechanics
sucessfully described a great body of scientific observations with plausibility and
precision.
it is possible that new experimental evidence could require a reformulation of the
laws of thermodynamics. Up to now this has not been necessary, although the
discovery of nuclear energy has had to be accommodated by expanding the framework
established in the 19th century.
1. there exists a property of the universe, called its energy, with cannot change
no matter what processes occur.
2. there exists a property of the universe, called its entropy, which always
changes in the same direction no matter what processes occur.
3. there exists a lower limit to the temperature that can be attained by matter,
called the absolute zero of temperature, and the entropy of all substances is the
same at that temperature

A "zeroth law of thermodynamics" is frequently cited, which acknowledges that a

temperature scale exits for all substances in nature and provides an absolute
measure of their tendencies to exchange heat.

energy has achieved the status of a household, in every day use. It is thought too
be a common sense concept with attendant intuitive meaning. a careful examination
of the concept of energy in all of its diverse aspects reveals that such an
intuition is superficial and potentially misleading.
for example, try to visualize the intuitive meaning of kinetic energy, a quantity
which implicitly contains the "square of the rate of displacement" of the matter in
a system.

fortunately, from a practical point of view, an intuitive understanding of what

energy is, is not crucial. Energy can be defined both physically and mathematically
and can be measured with precision. The description of the state of a system and
the prediction of its behavior rests upon the mathematical and physical formulation
of the concept, not on an intuitive understanding of it.

three broad categories of energy have been identified in scientific experience:

1. kinetic energy, which is associated with the motion, translation, or rotation,

of a particle or body and nothing else.
2. potential energy, which is associated with the position of a particle or body in
a potential field and nothing else.
3. internal energy, which is associated with the internal condition of the body and
does not otherwise depend upon its motion or position in space.

Thermodynamics at first focuses upon the influences that change the internal
condition of a system at rest. The apparatus ultimately is extended to include
potential and kinetic energ as well as internal energy.

in its most pretentious form the first law may be stated for the behavior of the
universe. In practical applications the focus of attention is on some small subset
of the universe, called "the system".

except for the case of a system which is isolated from its surroundings, changes
that occur inside the system are always accompanied by changes in the condition of
the matter in the vicinity of the system. The part of the universe that is external
to the system but is also affected by changes that are caused to occur in the
system is called "the surroundings". Thus, from the standpoint of any particular
process that may occur in practice, the sum of the changes that occur in the system
and the surroundings includes all of the changes in the universe associated with
that process.

by the first law the total energy of the universe cannot change for any process.
Energy can be transported, or converted from one form to another but cannot be
created or destroyed. Since conversion of energy from one form to another does not
change the total quantity of energy, the only way that the internal energy os a
system can change is by transferring energy across its boundary.

A mathematical statement of the first law for a system can thus be formulated from
the statement that the change in internal energy of a sytem for a process must be
equal to the sum of all energy transfers across the boundary of the system during
the process. It is only necessary to enumerate all of the possible kinds of energy
transfers that may occur for the class of system being considered and set the sum
of these energy transfers equal to the change in internal energy for the system for
the process.

let "U" be a thermodynamic state function called the internal energy of the system.
For any process, define ΔU to be increase in the internal energy of the system.
Enumerate all of the kinds of energy transfers that may occur:

"Q" is quantity of heat that flows into the system during the process.
"W" is defined to be the mechanical work done on the system by the force exerted by
the external pressure in the surroundings.
"w'" is defined to be all other kinds of work done on the system during the
process.

note that in introducing these definitions it was necessary to establish

conventions for the sign of each quantity. if "Q' is positiive, heat (and thus
energy) flows into the system, increasing ist internal energy; if for a given
process heat flows out of the system, "Q" is negative. Similarly, if "W" is
positive, the surroundings does work on the system and energy flows into the
system. If for the process under consideration work is done by the system on the
surroundings, W is negative and energy is transferred out of system. The statement
that the increase in the internal energy of the system during a process is the sum
os the transfers across the boundary may be written:

This is a mathematical statement of the first law of thermodynamics. In order to

apply it in practice, it will be necessary to devise an apparatus for evaluating
the process variables, Q, W e W for each kind of proccess that may be encountered
be each class of system.

In order to follow the course of a process in detail it is useful to consider it as

a succession of incremental steps, which produce infinitesimal changes in the
internal condition of the system and result from infinitesimal transfers of heat
and work across the boundary. The first law is pervasive; it applies not only to
the overall finite changes that a system and may experience but also to each
incremental step along the way. Energy must be conserved during each small
incremental step in a process.

thus, for an infinitesimal change in the conditions of the system,

where dU is the change in the state function U for an infinitesimal step in the
process, and dQ, dW and dW' are incremental quantities of heat and work that are
transferred across the boundary of the system.
It is widely accepted in thermodynamics that an infinitesimal quantify designated
by a d, as in dU, represents the change in a state function and thus has the
mathematical properties of denotes in infinitesimal quantity of heat or work;
however, these infinitesimal quantities do not have the mathematical properties of
a differential of a function implied by the operator, d. There is no mathematical
function of the state os the system, Q, of which dQ is differential, because Q is
not a state function; it has meaning only for a process.

Thus U is a state function, while Q, W and W' are process variable. Q, W e W' have
values that depend explicitly upon the path, i.e., the sequence of thermodynamic
states, traversed by the system during the process; ΔU depends only on the initial
and final states and is independent of the sequence of states that connect them.

3.2 The second law of thermodynamics

It is a common observation in human experience that processes observed in nature

have a natural direction of change. If a motion picture or videotape ir run
backwards, it's will be immediately evident to any viewer that something is wrong
with the motions perceived. A pebble dropped into a pound produces a splash and a
set of ripples that dissipate at the pond's edges. Viewed in reverse, ripples of
waves spontaneously generate at the edges of the pond, converge to the middle, and
amid an eruption of water, toss a pebble into the air. Energy is conserved in both
processes, but the second one will never occur; there is something about it which
is obviously contrary to experience.
When processes in nature are examined, either macroscopically or in detail, it is
found that this principle of a proper direction for change is pervasive.

similar to the first law, the second law of thermodynamics is general and
pervasive. No step in any process is exempt from its application. It applies
microscopically to every volume element in a system that is experiencing change, as
well as macroscopically to the system as a whole. it applies during each
infinitesimal increment of time in the process, as well as to the process as a
whole. Specifically stated, in every volume element of any system and surroundings
that may be experiencing change, at every instant in time, the entropy production
is posisitive. It will now be demonstrated that this does not imply that the
entropy of a system can only increase.

similar to energy, entropy changes arise from influences that operate to change the
condition of a system. However, the relationship between the entropy changes and
the influences that act is not the same as it is for energy. Just as with energy,
entropy can be transferred across the boundary of a system in association with
heat, work and massa transfers.

Unlike energy, the change in entropy of a system is not restricted to entropy

transferred across its boundaries. There is an additional contribution; namely, the
production of entropy inside the system. The first law is a conservation law, the
second law is not.
the transfer term may be positive or negative depending upon the nature of the
process and the flows at the boundary of the system. The second law states that,
for all processes for all systems

whether ΔS is positive or negative depends upon the sign of ΔS as well as its

relative magnitude in comparison with ΔSp. Thus, it is not unusual for the entropy
of a system to decrease for a given process. Ideed, many of the practical processes
that make technology work are explicitly set up to produce a negative change in
entropy of a system, i.e., to make a system change in a direction which is opposite
to that which would occur "naturraly". In order to accomplish this it is necessary
to place the system in an environment - a surroundings - that is capable of causing
the transfers necessary to produce the "unnatural" change.

the second law states that both of these production terms are positive. Thus, while
the entropy of a system may increase or decrease during a process, the entropy of
the universe, taken as system plus whatever surrouding are involved in producing
the changes within the system, can only increase.

these statements about entropy have been presented for a finite change in the
condition of a system. They may also be applied to an infinitesimal step in the
course of this change, for which the entropy changes are infinitesimals:

in which may be positive or negative but, by the second law,

3. intuitive meaning of entropy production

It is a tautology to state that all changes that occur in the universe are
spontaneous. To state that a given system placed in a given surroundings will
experience a specific process spontaneously merely acknowledges that for that
system in that surroundings that process will happen and not its reverse, or some
other process.