Prior to the 19th century, it was
believed that the sense of how hot or cold an object felt was determined
by how much "heat" it contained. Heat was envisioned as
a liquid that flowed from a hotter to a colder object; this weightless
fluid was called "caloric", and until the writings of
Joseph Black (1728-1799), no distinction was made between heat and
temperature. Black distinguished between the quantity (caloric)
and the intensity (temperature) of heat.
Benjamin Thomson, Count Rumford, published a paper
in 1798 entitled "an Inquiry Concerning the Source of Heat
which is Excited by Friction". Rumford had noticed the large
amount of heat generated when a cannon was drilled. He doubted that
a material substance was flowing into the cannon and concluded "it
appears to me to be extremely difficult if not impossible to form
any distinct idea of anything capable of being excited and communicated
in the manner the heat was excited and communicated in these experiments
except motion."
But it was not until J. P. Joule published a definitive
paper in 1847 that the the caloric idea was abandoned. Joule conclusively
showed that heat was a form of energy. As a result of the experiments
of Rumford, Joule, and others, it was demonstrated (explicitly stated
by Helmholtz in 1847), that the various forms of energy can be transformed
one into another.
When heat is transformed into any other
form of energy, or when other forms of energy are transformed into
heat, the total amount of energy (heat plus other forms) in the
system is constant.
This is the first law of thermodynamics,
the conservation of energy. To express it another way: it is in
no way possible either by mechanical, thermal, chemical, or other
means, to obtain a perpetual motion machine; i.e., one that creates
its own energy (except in the fantasy world of Maurits Escher's
"Waterfall"!)
A second statement may also be made about how
machines operate. A steam engine uses a source of heat to produce
work. Is it possible to completely convert the heat energy into
work, making it a 100% efficient machine? The answer is to be found
in the second law of thermodynamics:
No cyclic machine can convert heat energy
wholly into other forms of energy. It is not possible to construct
a cyclic machine that does nothing but withdraw heat energy and
convert it into mechanical energy.
The second law of thermodynamics implies the irreversibility
of certain processes - that of converting all heat into mechanical
energy, although it is possible to have a cyclic machine that does
nothing but convert mechanical energy into heat!
Sadi Carnot (1796-1832) conducted theoretical
studies of the efficiencies of heat engines (a machine which converts
some of its heat into useful work). He was trying to model the most
efficient heat engine possible. His theoretical work provided the
basis for practical improvements in the steam engine and also laid
the foundations of thermodynamics. He described an ideal engine,
called the Carnot engine, that is the most efficient way an engine
can be constructed. He showed that the efficiency of such an engine
is given by
efficiency = 1 - T"/T',
where the temperatures, T' and T" , are the
hot and cold "reservoirs" , respectively, between which
the machine operates. On this temperature scale, a heat engine whose
coldest reservoir is zero degrees would operate with 100% efficiency.
This is one definition of absolute zero, and it can be shown to
be identical to the absolute zero we discussed previously. The temperature
scale is called the absolute, the thermodynamic,
or the kelvin scale.
The way that the gas temperature scale and the
thermodynamic temperature scale are shown to be identical is based
on the microscopic interpretation of temperature, which postulates
that the macroscopic measurable quantity called temperature is a
result of the random motions of the microscopic particles that make
up a system.
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