In thermodynamics, the triple point of a substance is the temperature and pressure at which the three phases (gas, liquid, and solid) of that substance coexist in thermodynamic equilibrium. [1] It is that temperature and pressure at which the sublimation, fusion, and vaporisation curves meet. For example, the triple point of mercury occurs at a temperature of −38.8 °C (−37.8 °F) 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 unusual in that it has no sublimation/deposition curve and therefore no triple points where its solid phase meets its gas phase. Instead, it has a vapor-liquid-superfluid point, a solid-liquid-superfluid point, a solid-solid-liquid point, and a solid-solid-superfluid point. None of these should be confused with the Lambda Point, which is not any kind of triple point.
The term "triple point" was coined in 1873 by James Thomson, brother of Lord Kelvin. [2] The triple points of several substances are used to define points in the ITS-90 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).
Before 2019, the triple point of water was used to define the kelvin, the base unit of thermodynamic temperature in the International System of Units (SI). [3] The kelvin was defined so that the triple point of water is exactly 273.16 K, but that changed with the 2019 revision of the SI, where the kelvin was redefined so that the Boltzmann constant is exactly 1.380649×10−23 J⋅K−1, and the triple point of water became an experimentally measured constant.
Following the 2019 revision of the SI, the value of the triple point of water is no longer used as a defining point. However, its empirical value remains important: the unique combination of pressure and temperature at which liquid water, solid ice, and water vapor coexist in a stable equilibrium is approximately 273.16±0.0001 K [4] and a vapor pressure of 611.657 pascals (6.11657 mbar; 0.00603659 atm). [5] [6]
Liquid water can only exist at pressures equal to or greater than the triple point. Below this, in the vacuum of outer space, solid ice sublimates, transitioning directly into water vapor when heated at a constant pressure. Conversely, above the triple point, solid ice first melts into liquid water upon heating at a constant pressure, then evaporates or boils to form vapor at a higher temperature.
For most substances, the gas–liquid–solid triple point is the minimum temperature where the liquid can exist. For water, this is not the case. The melting point of ordinary ice decreases with pressure, as shown by the phase diagram's dashed green line. Just below the triple point, compression at a constant temperature transforms water vapor first to solid and then to liquid.
Historically, during the Mariner 9 mission to Mars, the triple point pressure of water was used to define "sea level". Now, laser altimetry and gravitational measurements are preferred to define Martian elevation. [7]
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 (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 251–273 K, ice I is formed first, followed by liquid water and then ice III or ice V, followed by other still denser high-pressure forms.
Phases in stable equilibrium | Pressure | Temperature |
---|---|---|
liquid water, ice Ih, and water vapor | 611.657 Pa [8] | 273.16 K (0.01 °C) |
liquid water, ice Ih, and ice III | 209.9 MPa | 251 K (−22 °C) |
liquid water, ice III, and ice V | 350.1 MPa | −17.0 °C |
liquid water, ice V, and ice VI | 632.4 MPa | 0.16 °C |
ice Ih, Ice II, and ice III | 213 MPa | −35 °C |
ice II, ice III, and ice V | 344 MPa | −24 °C |
ice II, ice V, and ice VI | 626 MPa | −70 °C |
Triple-point cells are used in the calibration 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, neon, oxygen, argon, mercury, and water for delineating six of its defined temperature 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 (now NIST, National Institute of Standards and Technology). [9]
Substance | T[ K ] (°C) | p[ kPa ]* (atm) |
---|---|---|
Acetylene | 192.4 K (−80.7 °C) | 120 kPa (1.2 atm) |
Ammonia | 195.40 K (−77.75 °C) | 6.060 kPa (0.05981 atm) |
Argon | 83.8058 K (−189.3442 °C) | 68.9 kPa (0.680 atm) |
Arsenic | 1,090 K (820 °C) | 3,628 kPa (35.81 atm) |
Butane [10] | 134.6 K (−138.6 °C) | 7×10−4 kPa (6.9×10−6 atm) |
Carbon (graphite) | 4,765 K (4,492 °C) | 10,132 kPa (100.00 atm) |
Carbon dioxide | 216.55 K (−56.60 °C) | 517 kPa (5.10 atm) |
Carbon monoxide | 68.10 K (−205.05 °C) | 15.37 kPa (0.1517 atm) |
Chloroform [11] [12] | 209.61 K (−63.54 °C) | ? |
Deuterium | 18.63 K (−254.52 °C) | 17.1 kPa (0.169 atm) |
Ethane | 89.89 K (−183.26 °C) | 1.1×10−3 kPa (1.1×10−5 atm) |
Ethanol [13] | 150 K (−123 °C) | 4.3×10−7 kPa (4.2×10−9 atm) |
Ethylene | 104.0 K (−169.2 °C) | 0.12 kPa (0.0012 atm) |
Formic acid [14] | 281.40 K (8.25 °C) | 2.2 kPa (0.022 atm) |
Helium-4 (vapor−He-I−He-II) [15] | 2.1768 K (−270.9732 °C) | 5.048 kPa (0.04982 atm) |
Helium-4 (hcp−bcc−He-II) [16] | 1.463 K (−271.687 °C) | 26.036 kPa (0.25696 atm) |
Helium-4 (bcc−He-I−He-II) [16] | 1.762 K (−271.388 °C) | 29.725 kPa (0.29336 atm) |
Helium-4 (hcp−bcc−He-I) [16] | 1.772 K (−271.378 °C) | 30.016 kPa (0.29623 atm) |
Hexafluoroethane [17] | 173.08 K (−100.07 °C) | 26.60 kPa (0.2625 atm) |
Hydrogen | 13.8033 K (−259.3467 °C) | 7.04 kPa (0.0695 atm) |
Hydrogen-1 (Protium) [18] | 13.96 K (−259.19 °C) | 7.18 kPa (0.0709 atm) |
Hydrogen chloride | 158.96 K (−114.19 °C) | 13.9 kPa (0.137 atm) |
Iodine [19] | 386.65 K (113.50 °C) | 12.07 kPa (0.1191 atm) |
Isobutane [20] | 113.55 K (−159.60 °C) | 1.9481×10−5 kPa (1.9226×10−7 atm) |
Krypton | 115.76 K (−157.39 °C) | 74.12 kPa (0.7315 atm) |
Mercury | 234.3156 K (−38.8344 °C) | 1.65×10−7 kPa (1.63×10−9 atm) |
Methane | 90.68 K (−182.47 °C) | 11.7 kPa (0.115 atm) |
Neon | 24.5561 K (−248.5939 °C) | 43.332 kPa (0.42765 atm) |
Nitric oxide | 109.50 K (−163.65 °C) | 21.92 kPa (0.2163 atm) |
Nitrogen | 63.18 K (−209.97 °C) | 12.6 kPa (0.124 atm) |
Nitrous oxide | 182.34 K (−90.81 °C) | 87.85 kPa (0.8670 atm) |
Oxygen | 54.3584 K (−218.7916 °C) | 0.14625 kPa (0.0014434 atm) |
Palladium | 1,825 K (1,552 °C) | 3.5×10−3 kPa (3.5×10−5 atm) |
Platinum | 2,045 K (1,772 °C) | 2×10−4 kPa (2.0×10−6 atm) |
Radon | 202 K (−71 °C) | 70 kPa (0.69 atm) |
(mono)Silane [21] | 88.48 K (−184.67 °C) | 0.019644 kPa (0.00019387 atm) |
Sulfur dioxide | 197.69 K (−75.46 °C) | 1.67 kPa (0.0165 atm) |
Titanium | 1,941 K (1,668 °C) | 5.3×10−3 kPa (5.2×10−5 atm) |
Uranium hexafluoride | 337.17 K (64.02 °C) | 151.7 kPa (1.497 atm) |
Water [5] [6] | 273.16 K (0.01 °C) | 0.611657 kPa (0.00603659 atm) |
Xenon | 161.3 K (−111.8 °C) | 81.5 kPa (0.804 atm) |
Zinc | 692.65 K (419.50 °C) | 0.065 kPa (0.00064 atm) |
Notes:
The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid and the liquid changes into a vapor.
In the physical sciences, a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is a different material, in its own separate phase.
In physics, a vapor or vapour is a substance in the gas phase at a temperature lower than its critical temperature, which means that the vapor can be condensed to a liquid by increasing the pressure on it without reducing the temperature of the vapor. A vapor is different from an aerosol. An aerosol is a suspension of tiny particles of liquid, solid, or both within a gas.
In physics, a state of matter is one of the distinct forms in which matter can exist. Four states of matter are observable in everyday life: solid, liquid, gas, and plasma. Many intermediate states are known to exist, such as liquid crystal, and some states only exist under extreme conditions, such as Bose–Einstein condensates and Fermionic condensates, neutron-degenerate matter, and quark–gluon plasma.
In thermodynamics, the enthalpy of vaporization, also known as the (latent) heat of vaporization or heat of evaporation, is the amount of energy (enthalpy) that must be added to a liquid substance to transform a quantity of that substance into a gas. The enthalpy of vaporization is a function of the pressure and temperature at which the transformation takes place.
Vapor pressure or equilibrium vapor pressure is the pressure exerted by a vapor in thermodynamic equilibrium with its condensed phases at a given temperature in a closed system. The equilibrium vapor pressure is an indication of a liquid's thermodynamic tendency to evaporate. It relates to the balance of particles escaping from the liquid in equilibrium with those in a coexisting vapor phase. A substance with a high vapor pressure at normal temperatures is often referred to as volatile. The pressure exhibited by vapor present above a liquid surface is known as vapor pressure. As the temperature of a liquid increases, the attractive interactions between liquid molecules become less significant in comparison to the entropy of those molecules in the gas phase, increasing the vapor pressure. Thus, liquids with strong intermolecular interactions are likely to have smaller vapor pressures, with the reverse true for weaker interactions.
Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics.
A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions at which thermodynamically distinct phases occur and coexist at equilibrium.
Latent heat is energy released or absorbed, by a body or a thermodynamic system, during a constant-temperature process—usually a first-order phase transition, like melting or condensation.
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 F is the number of degrees of freedom, C is the number of components and P is the number of phases, then
Sublimation is the transition of a substance directly from the solid to the gas state, without passing through the liquid state. The verb form of sublimation is sublime, or less preferably, sublimate. Sublimate also refers to the product obtained by sublimation. The point at which sublimation occurs rapidly is called critical sublimation point, or simply sublimation point. Notable examples include sublimation of dry ice at room temperature and atmospheric pressure, and that of solid iodine with heating.
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 approximation of thermodynamic temperature that facilitates the comparability and compatibility of temperature measurements internationally. It defines fourteen calibration points ranging from 0.65 K to 1357.77 K and is subdivided into multiple temperature ranges which overlap in some instances. ITS-90 is the most recent of a series of International Temperature Scales adopted by the CIPM since 1927. Adopted at the 1989 General Conference on Weights and Measures, it supersedes the International Practical Temperature Scale of 1968 and the 1976 "Provisional 0.5 K to 30 K Temperature Scale". The CCT has also published several online guidebooks to aid realisations of the ITS-90. The lowest temperature covered by the ITS-90 is 0.65 K. In 2000, the temperature scale was extended further, to 0.9 mK, by the adoption of a supplemental scale, known as the Provisional Low Temperature Scale of 2000 (PLTS-2000).
In thermodynamics, a critical point is the end point of a phase equilibrium curve. One example is the liquid–vapor critical point, the end point of the pressure–temperature curve that designates conditions under which a liquid and its vapor can coexist. At higher temperatures, the gas comes into a supercritical phase, and so cannot be liquefied by pressure alone. At the critical point, defined by a critical temperatureTc and a critical pressurepc, phase boundaries vanish. Other examples include the liquid–liquid critical points in mixtures, and the ferromagnet–paramagnet transition in the absence of an external magnetic field.
This page provides supplementary data to the article properties of water.
In chemistry, volatility is a material quality which describes how readily a substance vaporizes. At a given temperature and pressure, a substance with high volatility is more likely to exist as a vapour, while a substance with low volatility is more likely to be a liquid or solid. Volatility can also describe the tendency of a vapor to condense into a liquid or solid; less volatile substances will more readily condense from a vapor than highly volatile ones. Differences in volatility can be observed by comparing how fast substances within a group evaporate when exposed to the atmosphere. A highly volatile substance such as rubbing alcohol will quickly evaporate, while a substance with low volatility such as vegetable oil will remain condensed. In general, solids are much less volatile than liquids, but there are some exceptions. Solids that sublimate such as dry ice or iodine can vaporize at a similar rate as some liquids under standard conditions.
Thermodynamic databases contain information about thermodynamic properties for substances, the most important being enthalpy, entropy, and Gibbs free energy. Numerical values of these thermodynamic properties are collected as tables or are calculated from thermodynamic datafiles. Data is expressed as temperature-dependent values for one mole of substance at the standard pressure of 101.325 kPa, or 100 kPa. Both of these definitions for the standard condition for pressure are in use.
In thermodynamics and chemical engineering, the vapor–liquid equilibrium (VLE) describes the distribution of a chemical species between the vapor phase and a liquid phase.
The kelvin is the base unit for temperature in the International System of Units (SI). The Kelvin scale is an absolute temperature scale that starts at the lowest possible temperature, taken to be 0 K. By definition, the Celsius scale and the Kelvin scale have the exact same magnitude; that is, a rise of 1 K is equal to a rise of 1 °C and vice versa, and any temperature in degrees Celsius can be converted to kelvin by adding 273.15.
Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making up a substance.
Water is a polar inorganic compound that is at room temperature a tasteless and odorless liquid, which is nearly colorless apart from an inherent hint of blue. It is by far the most studied chemical compound and is described as the "universal solvent" and the "solvent of life". It is the most abundant substance on the surface of Earth and the only common substance to exist as a solid, liquid, and gas on Earth's surface. It is also the third most abundant molecule in the universe.