Absolute zero

Absolute zero is the lowest limit of the

thermodynamic temperature scale, a state
at which the enthalpy and entropy of a
cooled ideal gas reach their minimum
value, taken as zero kelvins. The
fundamental particles of nature have
minimum vibrational motion, retaining only
quantum mechanical, zero-point energy-
induced particle motion. The theoretical
temperature is determined by
extrapolating the ideal gas law; by
international agreement, absolute zero is
taken as −273.15° on the Celsius scale
(International System of Units),[1][2] which
equals −459.67° on the Fahrenheit scale
(United States customary units or Imperial
units).[3] The corresponding Kelvin and
Rankine temperature scales set their zero
points at absolute zero by definition.
Zero kelvins (−273.15 °C) is defined as absolute zero.

It is commonly thought of as the lowest

temperature possible, but it is not the
lowest enthalpy state possible, because all
real substances begin to depart from the
ideal gas when cooled as they approach
the change of state to liquid, and then to
solid; and the sum of the enthalpy of
vaporization (gas to liquid) and enthalpy of
fusion (liquid to solid) exceeds the ideal
gas's change in enthalpy to absolute zero.
In the quantum-mechanical description,
matter (solid) at absolute zero is in its
ground state, the point of lowest internal
energy.
The laws of thermodynamics indicate that
absolute zero cannot be reached using
only thermodynamic means, because the
temperature of the substance being
cooled approaches the temperature of the
cooling agent asymptotically,[4] and a
system at absolute zero still possesses
quantum mechanical zero-point energy,
the energy of its ground state at absolute
zero. The kinetic energy of the ground
state cannot be removed.

Scientists and technologists routinely

achieve temperatures close to absolute
zero, where matter exhibits quantum
effects such as Bose–Einstein
condensate, superconductivity and
superfluidity.

Thermodynamics near
absolute zero
At temperatures near 0 K (−273.15 °C;
−459.67 °F), nearly all molecular motion
ceases and ΔS = 0 for any adiabatic
process, where S is the entropy. In such a
circumstance, pure substances can
(ideally) form perfect crystals as T → 0.
Max Planck's strong form of the third law
of thermodynamics states the entropy of a
perfect crystal vanishes at absolute zero in
which a perfect crystal is gone. The
original Nernst heat theorem makes the
weaker and less controversial claim that
the entropy change for any isothermal
process approaches zero as T → 0:

The implication is that the entropy of a

perfect crystal approaches a constant
value.

The Nernst postulate identifies

the isotherm T = 0 as coincident
with the adiabat S = 0, although
other isotherms and adiabats
are distinct. As no two adiabats
 intersect, no other adiabat can
intersect the T = 0 isotherm.
Consequently no adiabatic
process initiated at nonzero
temperature can lead to zero
temperature. (≈ Callen, pp. 189–
190)

A perfect crystal is one in which the

internal lattice structure extends
uninterrupted in all directions. The perfect
order can be represented by translational
symmetry along three (not usually
orthogonal) axes. Every lattice element of
the structure is in its proper place, whether
it is a single atom or a molecular grouping.
For substances that exist in two (or more)
stable crystalline forms, such as diamond
and graphite for carbon, there is a kind of
chemical degeneracy. The question
remains whether both can have zero
entropy at T = 0 even though each is
perfectly ordered.

Perfect crystals never occur in practice;

imperfections, and even entire amorphous
material inclusions, can and do get "frozen
in" at low temperatures, so transitions to
more stable states do not occur.

Using the Debye model, the specific heat

and entropy of a pure crystal are
proportional to T 3, while the enthalpy and
chemical potential are proportional to T 4.
(Guggenheim, p. 111) These quantities
drop toward their T = 0 limiting values and
approach with zero slopes. For the specific
heats at least, the limiting value itself is
definitely zero, as borne out by
experiments to below 10 K. Even the less
detailed Einstein model shows this curious
drop in specific heats. In fact, all specific
heats vanish at absolute zero, not just
those of crystals. Likewise for the
coefficient of thermal expansion.
Maxwell's relations show that various
other quantities also vanish. These
phenomena were unanticipated.
Since the relation between changes in
Gibbs free energy (G), the enthalpy (H) and
the entropy is

thus, as T decreases, ΔG and ΔH approach

each other (so long as ΔS is bounded).
Experimentally, it is found that all
spontaneous processes (including
chemical reactions) result in a decrease in
G as they proceed toward equilibrium. If
ΔS and/or T are small, the condition
ΔG < 0 may imply that ΔH < 0, which would
indicate an exothermic reaction. However,
this is not required; endothermic reactions
can proceed spontaneously if the TΔS
term is large enough.

Moreover, the slopes of the derivatives of

ΔG and ΔH converge and are equal to zero
at T = 0. This ensures that ΔG and ΔH are
nearly the same over a considerable range
of temperatures and justifies the
approximate empirical Principle of
Thomsen and Berthelot, which states that
the equilibrium state to which a system
proceeds is the one that evolves the
greatest amount of heat, i.e., an actual
process is the most exothermic one.
(Callen, pp. 186–187)
One model that estimates the properties
of an electron gas at absolute zero in
metals is the Fermi gas. The electrons,
being Fermions, must be in different
quantum states, which leads the electrons
to get very high typical velocities, even at
absolute zero. The maximum energy that
electrons can have at absolute zero is
called the Fermi energy. The Fermi
temperature is defined as this maximum
energy divided by Boltzmann's constant,
and is of the order of 80,000 K for typical
electron densities found in metals. For
temperatures significantly below the Fermi
temperature, the electrons behave in
almost the same way as at absolute zero.
This explains the failure of the classical
equipartition theorem for metals that
eluded classical physicists in the late 19th
century.

Relation with Bose–Einstein

condensate

Velocity-distribution data of a gas of rubidium atoms

at a temperature within a few billionths of a degree
above absolute zero. Left: just before the appearance
of a Bose–Einstein condensate. Center: just after the
appearance of the condensate. Right: after further
evaporation, leaving a sample of nearly pure
condensate.
condensate.

A Bose–Einstein condensate (BEC) is a

state of matter of a dilute gas of weakly
interacting bosons confined in an external
potential and cooled to temperatures very
near absolute zero. Under such conditions,
a large fraction of the bosons occupy the
lowest quantum state of the external
potential, at which point quantum effects
become apparent on a macroscopic
scale.[5]

This state of matter was first predicted by

Satyendra Nath Bose and Albert Einstein in
1924–25. Bose first sent a paper to
Einstein on the quantum statistics of light
quanta (now called photons). Einstein was
impressed, translated the paper from
English to German and submitted it for
Bose to the Zeitschrift für Physik, which
published it. Einstein then extended Bose's
ideas to material particles (or matter) in
two other papers.[6]

Seventy years later, in 1995, the first

gaseous condensate was produced by Eric
Cornell and Carl Wieman at the University
of Colorado at Boulder NIST-JILA lab,
using a gas of rubidium atoms cooled to
170 nanokelvins (nK)[7] (1.7 × 10−7 K).[8]
A record cold temperature of 450 ±
80 picokelvins (pK) (4.5 × 10−10 K) in a BEC
of sodium atoms was achieved in 2003 by
researchers at Massachusetts Institute of
Technology (MIT).[9] The associated black-
body (peak emittance) wavelength of
6,400 kilometers is roughly the radius of
Earth.

Absolute temperature scales

Absolute, or thermodynamic, temperature
is conventionally measured in kelvins
(Celsius-scaled increments) and in the
Rankine scale (Fahrenheit-scaled
increments) with increasing rarity.
Absolute temperature measurement is
uniquely determined by a multiplicative
constant which specifies the size of the
degree, so the ratios of two absolute
temperatures, T2/T1, are the same in all
scales. The most transparent definition of
this standard comes from the Maxwell–
Boltzmann distribution. It can also be
found in Fermi–Dirac statistics (for
particles of half-integer spin) and Bose–
Einstein statistics (for particles of integer
spin). All of these define the relative
numbers of particles in a system as
decreasing exponential functions of
energy (at the particle level) over kT, with k
representing the Boltzmann constant and
T representing the temperature observed
at the macroscopic level.[1]

Negative temperatures
Temperatures that are expressed as
negative numbers on the familiar Celsius
or Fahrenheit scales are simply colder
than the zero points of those scales.
Certain systems can achieve truly negative
temperatures; that is, their thermodynamic
temperature (expressed in kelvins) can be
of a negative quantity. A system with a
truly negative temperature is not colder
than absolute zero. Rather, a system with a
negative temperature is hotter than any
system with a positive temperature, in the
sense that if a negative-temperature
system and a positive-temperature system
come in contact, heat flows from the
negative to the positive-temperature
system.[10]

Most familiar systems cannot achieve

negative temperatures because adding
energy always increases their entropy.
However, some systems have a maximum
amount of energy that they can hold, and
as they approach that maximum energy
their entropy actually begins to decrease.
Because temperature is defined by the
relationship between energy and entropy,
such a system's temperature becomes
negative, even though energy is being
added.[10] As a result, the Boltzmann factor
for states of systems at negative
temperature increases rather than
decreases with increasing state energy.
Therefore, no complete system, i.e.
including the electromagnetic modes, can
have negative temperatures, since there is
no highest energy state, so that the sum of
the probabilities of the states would
diverge for negative temperatures.
However, for quasi-equilibrium systems
(e.g. spins out of equilibrium with the
electromagnetic field) this argument does
not apply, and negative effective
temperatures are attainable.

On 3 January 2013, physicists announced

that for the first time they had created a
quantum gas made up of potassium
atoms with a negative temperature in
motional degrees of freedom.[11]

History

Robert Boyle pioneered the idea of an absolute zero

One of the first to discuss the possibility of
an absolute minimal temperature was
Robert Boyle. His 1665 New Experiments
and Observations touching Cold, articulated
the dispute known as the primum
frigidum.[12] The concept was well known
among naturalists of the time. Some
contended an absolute minimum
temperature occurred within earth (as one
of the four classical elements), others
within water, others air, and some more
recently within nitre. But all of them
seemed to agree that, "There is some body
or other that is of its own nature
supremely cold and by participation of
which all other bodies obtain that
quality."[13]

Limit to the "degree of cold" …

The question whether there is a limit to the

degree of coldness possible, and, if so,
where the zero must be placed, was first
addressed by the French physicist
Guillaume Amontons in 1702, in
connection with his improvements in the
air thermometer. His instrument indicated
temperatures by the height at which a
certain mass of air sustained a column of
mercury—the volume, or "spring" of the air
varying with temperature. Amontons
therefore argued that the zero of his
thermometer would be that temperature at
which the spring of the air was reduced to
nothing. He used a scale that marked the
boiling point of water at +73 and the
melting point of ice at +511⁄2, so that the
zero was equivalent to about −240 on the
Celsius scale.[14] Amontons held that the
absolute zero cannot be reached, so never
attempted to compute it explicitly.[15] The
value of −240 °C, or "431 divisions [in
Fahrenheit's thermometer] below the cold
of freezing water"[16] was published by
George Martine in 1740.
This close approximation to the modern
value of −273.15 °C[1] for the zero of the
air thermometer was further improved
upon in 1779 by Johann Heinrich Lambert,
who observed that −270 °C (−454.00 °F;
3.15 K) might be regarded as absolute
cold.[17]

Values of this order for the absolute zero

were not, however, universally accepted
about this period. Pierre-Simon Laplace
and Antoine Lavoisier, in their 1780
treatise on heat, arrived at values ranging
from 1,500 to 3,000 below the freezing
point of water, and thought that in any
case it must be at least 600 below. John
Dalton in his Chemical Philosophy gave ten
calculations of this value, and finally
adopted −3,000 °C as the natural zero of
temperature.

Lord Kelvin's work …

After James Prescott Joule had

determined the mechanical equivalent of
heat, Lord Kelvin approached the question
from an entirely different point of view, and
in 1848 devised a scale of absolute
temperature that was independent of the
properties of any particular substance and
was based on Carnot's theory of the
Motive Power of Heat and data published
by Henri Victor Regnault.[18] It followed
from the principles on which this scale
was constructed that its zero was placed
at −273 °C, at almost precisely the same
point as the zero of the air
thermometer.[14] This value was not
immediately accepted; values ranging
from −271.1 °C (−455.98 °F) to −274.5 °C
(−462.10 °F), derived from laboratory
measurements and observations of
astronomical refraction, remained in use in
the early 20th century.[19]

The race to absolute zero …

Commemorative plaque in Leiden

With a better theoretical understanding of

absolute zero, scientists were eager to
reach this temperature in the lab.[20] By
1845, Michael Faraday had managed to
liquefy most gases then known to exist,
and reached a new record for lowest
temperatures by reaching −130 °C
(−202 °F; 143 K). Faraday believed that
certain gases, such as oxygen, nitrogen,
and hydrogen, were permanent gases and
could not be liquefied.[21] Decades later, in
1873 Dutch theoretical scientist Johannes
Diderik van der Waals demonstrated that
these gases could be liquefied, but only
under conditions of very high pressure and
very low temperatures. In 1877, Louis Paul
Cailletet in France and Raoul Pictet in
Switzerland succeeded in producing the
first droplets of liquid air −195 °C
(−319.0 °F; 78.1 K). This was followed in
1883 by the production of liquid oxygen
−218 °C (−360.4 °F; 55.1 K) by the Polish
professors Zygmunt Wróblewski and Karol
Olszewski.
Scottish chemist and physicist James
Dewar and Dutch physicist Heike
Kamerlingh Onnes took on the challenge
to liquefy the remaining gases, hydrogen
and helium. In 1898, after 20 years of
effort, Dewar was first to liquefy hydrogen,
reaching a new low-temperature record of
−252 °C (−421.6 °F; 21.1 K). However,
Kamerlingh Onnes, his rival, was the first
to liquefy helium, in 1908, using several
precooling stages and the Hampson–
Linde cycle. He lowered the temperature to
the boiling point of helium −269 °C
(−452.20 °F; 4.15 K). By reducing the
pressure of the liquid helium he achieved
an even lower temperature, near 1.5 K.
These were the coldest temperatures
achieved on Earth at the time and his
achievement earned him the Nobel Prize in
1913.[22] Kamerlingh Onnes would
continue to study the properties of
materials at temperatures near absolute
zero, describing superconductivity and
superfluids for the first time.

Very low temperatures

The rapid expansion of gases leaving the Boomerang

 g g g
Nebula, a bi-polar, filamentary, likely proto-planetary
nebula in Centaurus, causes the lowest-observed
temperature outside a laboratory: 1 K

The average temperature of the universe

today is approximately 2.73 kelvins
(−270.42 °C; −454.76 °F), based on
measurements of cosmic microwave
background radiation.[23][24]

Absolute zero cannot be achieved,

although it is possible to reach
temperatures close to it through the use of
cryocoolers, dilution refrigerators, and
nuclear adiabatic demagnetization. The
use of laser cooling has produced
temperatures less than a billionth of a
kelvin.[25] At very low temperatures in the
vicinity of absolute zero, matter exhibits
many unusual properties, including
superconductivity, superfluidity, and
Bose–Einstein condensation. To study
such phenomena, scientists have worked
to obtain even lower temperatures.

The current world record was set in

1999 at 100 picokelvins (pK), or
0.0000000001 of a kelvin, by cooling the
nuclear spins in a piece of rhodium
metal.[26]
In November 2000, nuclear spin
temperatures below 100 pK were
reported for an experiment at the
Helsinki University of Technology's Low
Temperature Lab in Espoo, Finland.
However, this was the temperature of
one particular degree of freedom—a
quantum property called nuclear spin—
not the overall average thermodynamic
temperature for all possible degrees in
freedom.[27][28]
In February 2003, the Boomerang
Nebula was observed to have been
releasing gases at a speed of
500,000 km/h (310,000 mph) for the last
1,500 years. This has cooled it down to
approximately 1 K, as deduced by
astronomical observation, which is the
lowest natural temperature ever
recorded.[29]
In May 2005, the European Space
Agency proposed research in space to
achieve femtokelvin temperatures.[30]
In May 2006, the Institute of Quantum
Optics at the University of Hannover
gave details of technologies and
benefits of femtokelvin research in
space.[31]
In January 2013, physicist Ulrich
Schneider of the University of Munich in
Germany reported to have achieved
temperatures formally below absolute
zero ("negative temperature") in gases.
The gas is artificially forced out of
equilibrium into a high potential energy
state, which is, however, cold. When it
then emits radiation it approaches the
equilibrium, and can continue emitting
despite reaching formal absolute zero;
thus, the temperature is formally
negative.[32]
In September 2014, scientists in the
CUORE collaboration at the Laboratori
Nazionali del Gran Sasso in Italy cooled
a copper vessel with a volume of one
cubic meter to 0.006 kelvins
(−273.144 °C; −459.659 °F) for 15 days,
setting a record for the lowest
temperature in the known universe over
such a large contiguous volume.[33]
In June 2015, experimental physicists at
MIT cooled molecules in a gas of
sodium potassium to a temperature of
500 nanokelvins, and it is expected to
exhibit an exotic state of matter by
cooling these molecules a bit further.[34]
In 2017, Cold Atom Laboratory (CAL), an
experimental instrument is developed
for launch to the International Space
Station (ISS) in 2018.[35] The instrument
will create extremely cold conditions in
the microgravity environment of the ISS
leading to the formation of Bose–
 Einstein condensates that are a
magnitude colder than those that are
created in laboratories on Earth. In a
space-based laboratory, up to 20-second
interaction times and as low as 1
picokelvin ( K) temperatures are
achievable, and it could lead to
exploration of unknown quantum
mechanical phenomenæ and test some
of the most fundamental laws of
physics.[36][37]

See also
Absolute hot
Charles's law
 Heat
International Temperature Scale of 1990
Orders of magnitude (temperature)
Planck temperature
Thermodynamic temperature
Triple point
Ultracold atom
Kinetic energy
Entropy

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Ketterle, and Wieman Share Nobel
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Further reading
Herbert B. Callen (1960). "Chapter 10" .
Thermodynamics . New York: John Wiley
& Sons. ISBN 978-0-471-13035-2.
OCLC 535083 .
Herbert B. Callen (1985).
Thermodynamics and an Introduction to
Thermostatistics (Second ed.). New
York: John Wiley & Sons. ISBN 978-0-
471-86256-7.
E.A. Guggenheim (1967).
Thermodynamics: An Advanced
Treatment for Chemists and Physicists
(Fifth ed.). Amsterdam: North Holland
Publishing. ISBN 978-0-444-86951-7.
OCLC 324553 .
George Stanley Rushbrooke (1949).
Introduction to Statistical Mechanics .
Oxford: Clarendon Press.
OCLC 531928 .
External links
"Absolute zero" : a two part NOVA
episode originally aired January 2008
"What is absolute zero?" Lansing State
Journal

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