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thermodynamics Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of th ...
, the triple point of a substance is the
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measurement, measured with a thermometer. Thermometers are calibrated in various Conversion of units of temperature, temp ...
and
pressure Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and e ...
at which the three phases (
gas Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma). A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
, liquid, and
solid Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structural ...
) of that substance coexist in thermodynamic equilibrium.. It is that temperature and pressure at which the sublimation curve,
fusion Fusion, or synthesis, is the process of combining two or more distinct entities into a new whole. Fusion may also refer to: Science and technology Physics *Nuclear fusion, multiple atomic nuclei combining to form one or more different atomic nucl ...
curve and the vaporisation curve meet. For example, the triple point of mercury occurs at a temperature of and a pressure of 0.165 m Pa. In addition to the triple point for solid, liquid, and gas phases, a triple point may involve more than one solid phase, for substances with multiple polymorphs. Helium-4 is a special case that presents a triple point involving two different fluid phases (
lambda point The lambda point is the temperature at which normal fluid helium (helium I) makes the transition to superfluid helium II (approximately 2.17 K at 1 atmosphere). The lowest pressure at which He-I and He-II can coexist is the vapor−He-I−He-II ...
). The triple point of
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
was used to define the
kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and phy ...
, the base unit of thermodynamic temperature in the International System of Units (SI). The value of the triple point of water was fixed by definition, rather than measured, but that changed with the
2019 redefinition of SI base units In 2019, four of the seven SI base units specified in the International System of Quantities were redefined in terms of natural physical constants, rather than human artifacts such as the standard kilogram. Effective 20 May 2019, the 144 ...
. The triple points of several substances are used to define points in the
ITS-90 The International Temperature Scale of 1990 (ITS-90) is an equipment calibration standard specified by the International Committee of Weights and Measures (CIPM) for making measurements on the Kelvin and Celsius temperature scales. It is an approx ...
international temperature scale, ranging from the triple point of hydrogen (13.8033 K) to the triple point of water (273.16 K, 0.01 °C, or 32.018 °F). The term "triple point" was coined in 1873 by James Thomson, brother of
Lord Kelvin William Thomson, 1st Baron Kelvin, (26 June 182417 December 1907) was a British mathematician, mathematical physicist and engineer born in Belfast. Professor of Natural Philosophy at the University of Glasgow for 53 years, he did important ...
.


Triple point of water


Gas–liquid–solid triple point

The single combination of pressure and temperature at which liquid
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
, solid
ice Ice is water frozen into a solid state, typically forming at or below temperatures of 0 degrees Celsius or Depending on the presence of impurities such as particles of soil or bubbles of air, it can appear transparent or a more or less opaqu ...
, and
water vapor (99.9839 °C) , - , Boiling point , , - , specific gas constant , 461.5 J/( kg·K) , - , Heat of vaporization , 2.27 MJ/kg , - , Heat capacity , 1.864 kJ/(kg·K) Water vapor, water vapour or aqueous vapor is the gaseous p ...
can coexist in a stable equilibrium occurs at exactly and a partial vapor pressure of .International Equations for the Pressure along the Melting and along the Sublimation Curve of Ordinary Water Substance
W. Wagner, A. Saul and A. Pruss (1994), J. Phys. Chem. Ref. Data, 23, 515.
At that point, it is possible to change all of the substance to ice, water, or vapor by making arbitrarily small changes in pressure and temperature. Even if the total pressure of a system is well above the triple point of water, provided that the partial pressure of the water vapor is 611.657  pascals, then the system can still be brought to the triple point of water. Strictly speaking, the surfaces separating the different phases should also be perfectly flat, to negate the effects of surface tension. The gas–liquid–solid triple point of water corresponds to the minimum pressure at which liquid water can exist. At pressures below the triple point (as in
outer space Outer space, commonly shortened to space, is the expanse that exists beyond Earth and its atmosphere and between celestial bodies. Outer space is not completely empty—it is a near-perfect vacuum containing a low density of particles, pred ...
), solid ice when heated at constant pressure is converted directly into water vapor in a process known as sublimation. Above the triple point, solid ice when heated at constant pressure first melts to form liquid water, and then evaporates or boils to form vapor at a higher temperature. For most substances the gas–liquid–solid triple point is also the minimum temperature at which the liquid can exist. For water, however, this is not true because the melting point of ordinary ice decreases as a function of pressure, as shown by the dashed green line in the phase diagram. At temperatures just below the triple point, compression at constant temperature transforms water vapor first to solid and then to liquid (water ice has lower density than liquid water, so increasing pressure leads to a liquefaction). The triple point pressure of water was used during the Mariner 9 mission to
Mars Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury. In the English language, Mars is named for the Roman god of war. Mars is a terrestrial planet with a thin at ...
as a reference point to define "sea level". More recent missions use laser altimetry and gravity measurements instead of pressure to define elevation on Mars.


High-pressure phases

At high pressures, water has a complex phase diagram with 15 known phases of ice and several triple points, including 10 whose coordinates are shown in the diagram. For example, the triple point at 251 K (−22 °C) and 210 MPa (2070 atm) corresponds to the conditions for the coexistence of
ice Ih Photograph showing details of an ice cube under magnification. Ice Ih is the form of ice commonly seen on Earth. Phase space of ice Ih with respect to other ice phases. Ice Ih (hexagonal ice crystal) (pronounced: ice one h, also known as ice-p ...
(ordinary ice), ice III and liquid water, all at equilibrium. There are also triple points for the coexistence of three solid phases, for example ice II, ice V and ice VI at 218 K (−55 °C) and 620 MPa (6120 atm). For those high-pressure forms of ice which can exist in equilibrium with liquid, the diagram shows that melting points increase with pressure. At temperatures above 273 K (0 °C), increasing the pressure on water vapor results first in liquid water and then a high-pressure form of ice. In the range , ice I is formed first, followed by liquid water and then ice III or ice V, followed by other still denser high-pressure forms.


Triple-point cells

Triple-point cells are used in the
calibration In measurement technology and metrology, calibration is the comparison of measurement values delivered by a device under test with those of a calibration standard of known accuracy. Such a standard could be another measurement device of kno ...
of thermometers. For exacting work, triple-point cells are typically filled with a highly pure chemical substance such as hydrogen, argon, mercury, or water (depending on the desired temperature). The purity of these substances can be such that only one part in a million is a contaminant, called "six nines" because it is 99.9999% pure. A specific isotopic composition (for water, VSMOW) is used because variations in isotopic composition cause small changes in the triple point. Triple-point cells are so effective at achieving highly precise, reproducible temperatures, that an international calibration standard for thermometers called ITS–90 relies upon triple-point cells of
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...
, neon,
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
,
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice as ...
, mercury, and
water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...
for delineating six of its defined temperature points.


Table of triple points

This table lists the gas–liquid–solid triple points of several substances. Unless otherwise noted, the data come from the U.S.
National Bureau of Standards The National Institute of Standards and Technology (NIST) is an agency of the United States Department of Commerce whose mission is to promote American innovation and industrial competitiveness. NIST's activities are organized into physical sci ...
(now NIST, National Institute of Standards and Technology). Notes: * For comparison, typical atmospheric pressure is 101.325 kPa (1 atm). * Before the new definition of SI units, water's triple point, 273.16 K, was an exact number.


See also

* Critical point (thermodynamics) *
Gibbs' phase rule In thermodynamics, the phase rule is a general principle governing "pVT" systems, whose thermodynamic states are completely described by the variables pressure (), volume () and temperature (), in thermodynamic equilibrium. If is the number of d ...


References


External links

* {{DEFAULTSORT:Triple Point Chemical properties Phase transitions Thermodynamics Threshold temperatures Gases 1873 introductions