The study of the laws that govern
the conversion of energy from one form to another, the direction
in which heat will flow, and the availability of energy to do work.
It is based on the concept that in an isolated system anywhere in
the universe there is a measurable quantity of energy called the
internal energy (U) of the system. This is the total kinetic and
potential energy of the atoms and molecules of the system of all
kinds that can be transferred directly as heat; it therefore excludes
chemical and nuclear energy. The value of U can only be changed
if the system ceases to be isolated. In these circumstances U can
change by the transfer of mass to or from the system, the transfer
of heat (Q) to or from the system, or by work (W) being done on
or by the system. For an adiabatic (Q=0) system of constant mass,
DU=W. By convention, W is taken to be positive if work s done on
the system and negative if work is done by the system. For nonadiabatic
systems of constant mass, DU = Q + W. This statement, which is equivalent
to the law of conservation of energy, is known as the first law
of thermodynamics.
All natural process conform to this law, but not
all processes conforming to it can occur in nature. Most natural
processes are irreversible, i.e. they will proceed in one direction.
The direction that a natural process can take is the subject of
the second law of thermodynamics, which can be stated in a variety
of ways. Rudolf Clausius stated the law in two ways: "heat
cannot be transferred from one body to a second body at a higher
temperature without producing some other effect" and "the
entropy of a closed system increases with time". These statements
introduce the thermodynamic concepts of temperature (T) and entropy
(S), both of which are parameters determining the direction in which
an irreversible process can go. The temperature of the body or system
determines whether heat will flow into it or out of it; its entropy
is a measure of the unavailability of its energy to do work. Thus
T and S determine the relationship between Q and W in the statement
of the first law. This is usually presented by stating the second
law in the form DU = TDS - W.
The second law if concerned with changes in entropy
(DS). The third law of thermodynamics provides an absolute scale
of values for entropy by stating that for changes involving only
perfect crystalline solids at absolute zero, the change of the total
entropy is zero. This law enables absolute values to be stated for
entropies.
One other law is used in thermodynamics. Because
it is fundamental to, and assumed by, the other laws of thermodynamics,
it is usually known as the zeroth law of thermodynamics. This law
states that when two bodies are each separately in thermal equilibrium
with a third body, then all three bodies are in thermal equilibrium.
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