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This article is about the thermodynamic property. For the constituent microscopic particles.
other uses, see Temperature (disambiguation).
1 Eects of temperature
Many physical processes are aected by temperature,
such as
2 Temperature scales
For an ideal gas, temperature is proportional to the aver- See also: Scale of temperature
age kinetic energy of the random microscopic motions of
1
Temperature scales dier in two ways: the point chosen ically older, while theoretically based scales arose in the
as zero degrees, and the magnitudes of incremental units middle of the nineteenth century.[2][3]
or degrees on the scale.
The Celsius scale (C) is used for common temperature
measurements in most of the world. It is an empirical
scale. It developed by a historical progress, which led to
its zero point 0C being dened by the freezing point of
water, with additional degrees dened so that 100C was
the boiling point of water, both at sea-level atmospheric
pressure. Because of the 100 degree interval, it is called a
centigrade scale.[1] Since the standardization of the kelvin
in the International System of Units, it has subsequently
been redened in terms of the equivalent xing points on
the Kelvin scale, and so that a temperature increment of
one degree Celsius is the same as an increment of one
kelvin, though they dier by an additive oset of 273.15.
Thermodynamic
temperature
approach
to
3.1
3.2
3
It is framed in terms of an idealized device called a Carnot
engine, imagined to dene a continuous cycle of states
of its working body. The cycle is imagined to run so
slowly that at each point of the cycle the working body
is in a state of thermodynamic equilibrium. There are
four limbs in such a Carnot cycle. The engine consists of
four bodies. The main one is called the working body.
Two of them are called heat reservoirs, so large that their
respective non-deformation variables are not changed by
transfer of energy as heat through a wall permeable only
to heat to the working body. The fourth body is able to
exchange energy with the working body only through adiabatic work; it may be called the work reservoir. The
substances and states of the two heat reservoirs should be
chosen so that they are not in thermal equilibrium with
one another. This means that they must be at dierent
xed temperatures, one, labeled here with the number
1, hotter than the other, labeled here with the number
2. This can be tested by connecting the heat reservoirs
successively to an auxiliary empirical thermometric body
that starts each time at a convenient xed intermediate
temperature. The thermometric body should be composed of a material that has a strictly monotonic relation
between its chosen empirical thermometric variable and
the amount of adiabatic isochoric work done on it. In order to settle the structure and sense of operation of the
Carnot cycle, it is convenient to use such a material also
for the working body; because most materials are of this
kind, this is hardly a restriction of the generality of this
denition. The Carnot cycle is considered to start from
an initial condition of the working body that was reached
by the completion of a reversible adiabatic compression.
From there, the working body is initially connected by a
wall permeable only to heat to the heat reservoir number
1, so that during the rst limb of the cycle it expands and
does work on the work reservoir. The second limb of the
cycle sees the working body expand adiabatically and reversibly, with no energy exchanged as heat, but more energy being transferred as work to the work reservoir. The
third limb of the cycle sees the working body connected,
through a wall permeable only to heat, to the heat reservoir 2, contracting and accepting energy as work from
the work reservoir. The cycle is closed by reversible adiabatic compression of the working body, with no energy
transferred as heat, but energy being transferred to it as
work from the work reservoir.
Then the absolute or thermodynamic temperatures, T 1 The zeroth law of thermodynamics allows this denition
and T 2 , of the reservoirs are dened so that to be such to be used to measure the absolute or thermodynamic
that
temperature of an arbitrary body of interest, by making
the other heat reservoir have the same temperature as the
body of interest.
T1 /T2 = Q1 /Q2 .
(1)
Kelvins original work postulating absolute temperature
was published in 1848. It was based on the work of
Carnot, before the formulation of the rst law of thermodynamics. Kelvin wrote in his 1848 paper that his scale
was absolute in the sense that it was dened independently of the properties of any particular kind of matter. His denitive publication, which sets out the denition just stated, was printed in 1853, a paper read in
1851.[15][16][17][18]
This denition rests on the physical assumption that
there are readily available walls permeable only to heat.
In his detailed denition of a wall permeable only to
heat, Carathodory includes several ideas. The nondeformation state variable of a closed system is represented as a real number. A state of thermal equilibrium
between two closed systems connected by a wall permeable only to heat means that a certain mathematical
relation holds between the state variables, including the
respective non-deformation variables, of those two systems (that particular mathematical relation is regarded by
Buchdahl as a preferred statement of the zeroth law of
thermodynamics).[19] Also, referring to thermal contact
equilibrium, whenever each of the systems S 1 and S 2 is
made to reach equilibrium with a third system S 3 under
identical conditions, the systems S 1 and S 2 are in mutual
equilibrium.[20] It may be viewed as a re-statement of
the principle stated by Maxwell in the words: All heat is
of the same kind.[21] This physical idea is also expressed
by Bailyn as a possible version of the zeroth law of thermodynamics: All diathermal walls are equivalent.[22]
Thus the present denition of thermodynamic temperature rests on the zeroth law of thermodynamics. Explicitly, this present denition of thermodynamic temperature also rests on the rst law of thermodynamics, for the
determination of amounts of energy transferred as heat.
Implicitly for this denition, the second law of thermodynamics provides information that establishes the virtuous
character of the temperature so dened. It provides that
any working substance that complies with the requirement stated in this denition will lead to the same ratio of thermodynamic temperatures, which in this sense
is universal, or absolute. The second law of thermodynamics also provides that the thermodynamic temperature dened in this way is positive, because this denition
requires that the heat reservoirs not be in thermal equilibrium with one another, and the cycle can be imagined to
operate only in one sense if net work is to be supplied to
the work reservoir.
( U )
S V,N
(2) [25][26][27]
Likewise, when the body is described by stating its entropy S as a function of its internal energy U, and other
state variables V, N, with S = S (U, V, N), then the reciprocal of the temperature is equal to the partial derivative
of the entropy with respect to the internal energy:
1
T
( S )
U V,N
(3) [25][27][28]
The above denition, equation (1), of the absolute temperature is due to Kelvin. It refers to systems closed
to transfer of matter, and has special emphasis on directly experimental procedures. A presentation of thermodynamics by Gibbs starts at a more abstract level
and deals with systems open to the transfer of matter;
in this development of thermodynamics, the equations
(2) and (3) above are actually alternative denitions of
temperature.[29]
5
classical irreversible thermodynamics, a body is usually
spatially and temporally divided conceptually into 'cells
of small size. If classical thermodynamic equilibrium
conditions for matter are fullled to good approximation
in such a 'cell', then it is homogeneous and a temperature exists for it. If this is so for every 'cell' of the body,
then local thermodynamic equilibrium is said to prevail
throughout the body.[30][31][32][33][34]
5.1
For experimental physics, hotness means that, when comparing any two given bodies in their respective separate
thermodynamic equilibria, any two suitably given empirical thermometers with numerical scale readings will
agree as to which is the hotter of the two given bodies, or that they have the same temperature.[48] This does
not require the two thermometers to have a linear relation between their numerical scale readings, but it does
require that the relation between their numerical readings shall be strictly monotonic.[49][50] A denite sense of
greater hotness can be had, independently of calorimetry,
of thermodynamics, and of properties of particular materials, from Wiens displacement law of thermal radiation: the temperature of a bath of thermal radiation is
proportional, by a universal constant, to the frequency of
the maximum of its frequency spectrum; this frequency
is always positive, but can have values that tend to zero.
Thermal radiation is initially dened for a cavity in thermodynamic equilibrium. These physical facts justify a
mathematical statement that hotness exists on an ordered
one-dimensional manifold. This is a fundamental character of temperature and thermometers for bodies in their
own thermodynamic equilibrium.[2][37][38][51][52]
Except for a system undergoing a rst-order phase change
such as the melting of ice, as a closed system receives
heat, without change in its volume and without change in
external force elds acting on it, its temperature rises. For
a system undergoing such a phase change so slowly that
departure from thermodynamic equilibrium can be neglected, its temperature remains constant as the system is
supplied with latent heat. Conversely, a loss of heat from
a closed system, without phase change, without change of
volume, and without change in external force elds acting
on it, decreases its temperature.[53]
5.2
HEAT CAPACITY
While for bodies in their own thermodynamic equilibrium states, the notion of temperature requires that all
empirical thermometers must agree as to which of two
bodies is the hotter or that they are at the same temperature, this requirement is not safe for bodies that are in
steady states though not in thermodynamic equilibrium.
It can then well be that dierent empirical thermometers
disagree about which is the hotter, and if this is so, then at
least one of the bodies does not have a well dened absolute thermodynamic temperature. Nevertheless, any one
given body and any one suitable empirical thermometer
can still support notions of empirical, non-absolute, hotness and temperature, for a suitable range of processes.
This is a matter for study in non-equilibrium thermody-
6 Heat capacity
See also: Heat capacity and Calorimetry
When an energy transfer to or from a body is only as heat,
state of the body changes. Depending on the surroundings and the walls separating them from the body, various
changes are possible in the body. They include chemical
reactions, increase of pressure, increase of temperature,
and phase change. For each kind of change under specied conditions, the heat capacity is the ratio of the quantity of heat transferred to the magnitude of the change.
For example, if the change is an increase in temperature
7.1
Units
at constant volume, with no phase change and no chemical change, then the temperature of the body rises and its
pressure increases. The quantity of heat transferred, Q,
divided by the observed temperature change, T, is the
bodys heat capacity at constant volume, CV.
CV =
Q
T
Temperature measurement
See also: Timeline of temperature and pressure measurement technology, International Temperature Scale
of 1990 and Comparison of temperature scales
Temperature measurement using modern scientic
thermometers and temperature scales goes back at least
as far as the early 18th century, when Gabriel Fahrenheit
adapted a thermometer (switching to mercury) and
a scale both developed by Ole Christensen Rmer.
Fahrenheits scale is still in use in the United States for
non-scientic applications.
Temperature is measured with thermometers that may be
calibrated to a variety of temperature scales. In most
of the world (except for Belize, Myanmar, Liberia and
the United States), the Celsius scale is used for most
temperature measuring purposes. Most scientists measure temperature using the Celsius scale and thermodynamic temperature using the Kelvin scale, which is
the Celsius scale oset so that its null point is 0K =
273.15C, or absolute zero. Many engineering elds
in the U.S., notably high-tech and US federal specications (civil and military), also use the Kelvin and Celsius scales. Other engineering elds in the U.S. also
rely upon the Rankine scale (a shifted Fahrenheit scale)
when working in thermodynamic-related disciplines such
as combustion.
7.1
Units
Conversion
Plasma physics
THEORETICAL FOUNDATION
8.2
9
and that all energy is translational kinetic energy. Using
a sophisticated symmetry argument,[68] Boltzmann deduced what is now called the MaxwellBoltzmann probability distribution function for the velocity of particles
in an ideal gas. From that probability distribution function, the average kinetic energy, Ek (per particle), of a
monatomic ideal gas is:[64][69]
Ek =
1
3
mv 2 = kT ,
2 rms
2
pV = nRT
When two otherwise isolated bodies are connected together by a rigid physical path impermeable to matter,
there is spontaneous transfer of energy as heat from the
hotter to the colder of them. Eventually they reach a state
of mutual thermal equilibrium, in which heat transfer has
ceased, and the bodies respective state variables have settled to become unchanging.
10
8.3
THEORETICAL FOUNDATION
eciency =
qH qC
qC
wcy
=
= 1
qH
qH
qH
qC
= f (TH , TC )
qH
(5)
Carnots theorem states that all reversible engines operating between the same heat reservoirs are equally ecient.
Thus, a heat engine operating between T 1 and T 3 must
have the same eciency as one consisting of two cycles,
one between T 1 and T 2 , and the second between T 2 and
T 3 . This can only be the case if:
q13 =
q1 q2
q2 q3
which implies:
(6)
Substituting Equation 4 back into Equation 2 gives a relationship for the eciency in terms of temperature:
eciency = 1
qC
TC
= 1
qH
TH
(7)
=0
TH
TC
where the negative sign indicates heat ejected from the
system. This relationship suggests the existence of a state
function, S, dened by:
(4)
dq
where wcy is the work done per cycle. The eciency de- dS = rev
T
pends only on qC/qH. Because qC and qH correspond to
heat transfer at the temperatures TC and TH, respectively, where the subscript indicates a reversible process. The
change of this state function around any cycle is zero, as
qC/qH should be some function of these temperatures:
(8)
8.6
Negative temperature
is necessary for any state function. This function corresponds to the entropy of the system, which was described
previously. Rearranging Equation 6 gives a new denition for temperature in terms of entropy and heat:
11
has a sublimation temperature of 78.5C which is equivalent to 109.3F. On the absolute Kelvin scale, however,
this temperature is 194.6 K. On the absolute scale of thermodynamic temperature no material can have a temperature smaller than or equal to 0 K, both of which are forbidden by the third law of thermodynamics.
dqrev
dS
Temperature
is basically dened for a body in its own
(9)
state of internal thermodynamic equilibrium, and in this
For a system, where entropy S(E) is a function of its en- denition, on an absolute scale, it is always positive. In an
apparent contradiction of this reliable and valid rule, a soergy E, the temperature T is given by:
called negative absolute temperature may be approximately dened for a component of a body that is not in its
d
own state of internal thermodynamic equilibrium: a com1
T =
S(E)
(10)
ponent may have a negative approximate temperature
dE
while the rest of the components of the body have posii.e. the reciprocal of the temperature is the rate of intive approximate temperatures. Such a non-equilibrium
crease of entropy with respect to energy.
situation is either transient in time or is maintained by
external factors that drive a ow of energy through the
body of interest. An example of such a component is a
8.4 Denition from statistical mechanics
spin system within a body, as follows.
T =
Statistical mechanics denes temperature based on a systems fundamental degrees of freedom. Eq.(10) is the
dening relation of temperature. Eq. (9) can be derived
from the principles underlying the fundamental thermodynamic relation.
12
11
Examples of temperature
Planck temperature
Rankine scale
Relativistic heat conduction
Satellite temperature measurements
Stagnation temperature
Sea surface temperature
Thermal radiation
Thermoception
Thermodynamic (absolute) temperature
Thermography
Thermometer
Body temperature (thermoregulation)
Virtual temperature
Wet Bulb Globe Temperature
Wet-bulb temperature
10
See also
Scale of temperature
Atmospheric temperature
Color temperature
Dry-bulb temperature
Heat conduction
Heat convection
ISO 1
Instrumental temperature record
ITS-90
Laser Schlieren Deectometry
Maxwells demon
13
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ISBN 0-471-62430-6, pp. 49, 69.
[43] J. S. Dugdale (1996, 1998). Entropy and its Physical Interpretation. Taylor & Francis. p. 13. ISBN 978-0-74840569-5. Check date values in: |date= (help)
[26] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318797-3, pp. 1415, 214.
[27] Callen, H.B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (rst edition 1960), second
edition 1985, John Wiley & Sons, New York, ISBN 0
471862568, pp. 146148.
[28] Kondepudi, D., Prigogine, I. (1998). Modern Thermodynamics. From Heat Engines to Dissipative Structures, John
Wiley, Chichester, ISBN 0-471-97394-7, pp. 115116.
[29] Tisza, L. (1966). Generalized Thermodynamics, M.I.T.
Press, Cambridge MA, p. 58.
[45] M. J. Moran, H. N. Shapiro (2006). 1.6.1. Fundamentals of Engineering Thermodynamics (5 ed.). John Wiley
& Sons, Ltd. p. 14. ISBN 978-0-470-03037-0.
[46] T.W. Leland, Jr. Basic Principles of Classical and Statistical Thermodynamics (PDF). p. 14. Consequently
we identify temperature as a driving force which causes
something called heat to be transferred.
[47] Tait, P.G. (1884). Heat, Macmillan, London, Chapter
VII, pages 42, 103-117.
[30] Milne, E.A. (1929). The eect of collisions on monochromatic radiative equilibrium, Monthly Notices of the Royal
Astronomical Society, 88: 493502.
[48] Beattie, J.A., Oppenheim, I. (1979). Principles of Thermodynamics, Elsevier Scientic Publishing Company,
Amsterdam, 0444418067, page 29.
[33] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318797-3, pp. 133135.
[34] Callen, H.B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (rst edition 1960), second
edition 1985, John Wiley & Sons, New York, ISBN 0
471862568, pp. 309310.
[52] Pitteri, M. (1984). On the axiomatic foundations of temperature, Appendix G6 on pages 522-544 of Rational
Thermodynamics, C. Truesdell, second edition, Springer,
New York, ISBN 0-387-90874-9.
14
11
11.1
11.1
Adkins, C.J. (1968/1983). Equilibrium Thermodynamics, (1st edition 1968), third edition 1983, Cam-
15
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16
12
13
Further reading
Chang, Hasok (2004). Inventing Temperature: Measurement and Scientic Progress. Oxford: Oxford
University Press. ISBN 978-0-19-517127-3.
Zemansky, Mark Waldo (1964). Temperatures Very
Low and Very High. Princeton, N.J.: Van Nostrand.
13
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