The triple point of a substance is the unique temperature and pressure at which its solid, liquid, and gaseous phases coexist in thermodynamic equilibrium.[1] This point marks the intersection of the three phase boundaries on a phase diagram, where the solid-liquid, liquid-vapor, and solid-vapor equilibrium curves meet.[2]For most substances, the triple point represents a fundamental and invariant condition that is independent of external influences, making it a precise reference for thermodynamic studies.[2] It defines the lowest pressure at which the liquid phase can exist in equilibrium with the solid or vapor phases, and below this pressure, the substance cannot form a stable liquid regardless of temperature.[3]Helium is a notable exception in that it does not solidify at atmospheric pressure even near absolute zero, requiring applied pressure for the solid phase, but it has a triple point at approximately 2.18 K and 5.04 kPa.[4]The triple point holds significant practical importance, particularly for calibration in temperature measurement.[5] Historically, until the 2019 redefinition of the International System of Units (SI), the kelvin was defined such that the triple point of water occurs exactly at 273.16 K, serving as the anchor for the thermodynamic temperature scale.[5] Today, water triple-point cells are used to realize this temperature with high precision (approximately ±50 µK) for calibrating thermometers, involving the equilibrium of pure water's ice, liquid, and vapor phases at a pressure of 611.657 Pa.[5][6]Examples illustrate the variability of triple points across substances. For water, it occurs at 273.16 K and 0.6113 kPa, slightly above its normal freezing point of 0 °C.[2] Carbon dioxide's triple point is at 216.6 K and 518 kPa (or approximately -56.4 °C and 5.11 atm), above atmospheric pressure, which explains why dry ice sublimes at standard conditions without melting.[1][2]Nitrogen has a triple point at 63.15 K and 12.46 kPa, highlighting the low-temperature equilibrium typical of cryogenic substances.[2] Some substances exhibit multiple triple points if they have polymorphic solid phases, adding complexity to their phase behavior.[1]
Fundamentals of Triple Points
Definition and Physical Meaning
The triple point of a substance is the particular temperature and pressure at which three distinct phases—typically solid, liquid, and gas—coexist in thermodynamic equilibrium, such that the chemical potentials of each phase are equal and no spontaneous phase transition occurs between them. This condition represents an invariant state where the Gibbs free energy per particle is identical across the phases, allowing the substance to remain stable in all three forms simultaneously without any net mass transfer or energy change driving a shift to one phase over the others.[7]Physically, the triple point signifies a unique confluence of phase boundaries, where the effects of temperature and pressure balance the intermolecular forces precisely enough to sustain multiple phases. Unlike other equilibrium points along two-phase boundaries, the triple point is independent of the system's size or composition for a pure substance, making it a highly reproducible referencestate that highlights the constraints imposed by thermodynamic laws on phase behavior.[8] In a phase diagram, this manifests as the intersection of three boundary curves, marking the sole location where such coexistence is possible.[9]The concept of the triple point emerged in the context of 19th-century advances in phase equilibria, with James Clerk Maxwell contributing through his 1874 construction of a thermodynamic surface model that illustrated phase coexistence, including the triple point, by plotting energy, entropy, and volume coordinates.[10] The term "triple point" itself was first introduced by James Thomson in 1873 during discussions of heterogeneous equilibria.[11] Experimental confirmation for water's triple point followed in the late 19th century through vapor pressure and equilibrium studies, establishing its role as a benchmark.Due to this intrinsic reproducibility and invariance, the triple point serves as a fundamental calibration standard for temperature and pressure scales in metrology, providing a natural, substance-specific fixed point that ensures consistency across measurements without reliance on arbitrary conventions.[9]
Thermodynamic Conditions for Equilibrium
At the triple point, three distinct phases—denoted as α, β, and γ—coexist in stable thermodynamic equilibrium, requiring the chemical potential to be equal across all phases: μ_α = μ_β = μ_γ. This equality ensures that there is no net driving force for matter to transfer between phases. Additionally, the temperature T and pressure P must be uniform throughout the system to satisfy conditions of thermal and mechanical equilibrium.[7][12]The locations of the phase boundaries converging at the triple point are determined by the Clapeyron equation, which describes the slope of each boundary curve in the pressure-temperature plane:\frac{dP}{dT} = \frac{\Delta H}{T \Delta V}Here, ΔH is the enthalpy change and ΔV is the volume change associated with the phase transition between each pair of phases. The distinct slopes of the three boundary curves—arising from differences in ΔH and ΔV—uniquely fix the intersection point where all three coexist.[13]For a one-component system at the triple point, the Gibbs phase rule indicates zero degrees of freedom (F = 0), meaning both temperature and pressure are invariantly fixed, with no external variables available to adjust while maintaining the three-phaseequilibrium.[14][15]While triple points represent stable equilibria under these conditions, metastable states can occur if kinetic barriers hinder phase transformations, though the focus here remains on true thermodynamic stability.
Triple Points in Phase Diagrams
Representation and Interpretation
In a pressure-temperature (P-T) phase diagram for a one-component system, the triple point is visually represented as the unique intersection where the three phase boundary curves—solid-liquid, liquid-vapor, and solid-vapor—meet, forming a characteristic Y-shaped junction.[16] This configuration arises because the triple point marks the specific conditions under which the solid, liquid, and vapor phases coexist in thermodynamic equilibrium, with no degrees of freedom allowing variation in pressure or temperature without disrupting the balance.[17] The slopes of these boundaries reflect the Clapeyron equation, dictating how phase stability changes with pressure and temperature.[18]The position of the triple point divides the P-T diagram into distinct regions: areas of single-phase stability (solid, liquid, or vapor) separated by the boundary lines, and narrow two-phase coexistence zones along those lines.[19] Interpreting the diagram involves recognizing that traversing a boundary induces a phase transition; for instance, increasing temperature across the solid-liquid line at constant pressure above the triple point temperature leads to melting, while paths below it may result in sublimation if crossing the solid-vapor boundary.[20] This graphical tool thus predicts phase behavior for the substance under varying conditions, essential for understanding stability limits.[21]While the focus here is on unary systems, triple points in binary mixtures differ fundamentally, appearing as invariant points (often eutectics) in temperature-composition diagrams where three phases—typically two solids and a liquid—coexist, rather than in P-T space. Beyond the critical point in unary diagrams, the liquid-vapor distinction vanishes, resulting in a supercritical fluid phase where no separate liquid-gas boundary exists, thereby precluding additional triple points involving those phases.[22]
Gibbs Phase Rule Application
The Gibbs phase rule, developed by J. Willard Gibbs in the late 19th century, quantifies the degrees of freedom F available in a multiphase system at equilibrium as F = C - P + 2, where C is the number of independently variable components and P is the number of coexisting phases.[23] This rule arises from the thermodynamic constraints imposed by the equality of chemical potentials across phases and the conservation of mass.[24] For a triple point, defined by the coexistence of three phases (P = 3) in a single-component system (C = 1), the calculation yields F = 1 - 3 + 2 = 0, rendering the system invariant: both temperature T and pressure P are uniquely fixed, with no variables adjustable without disrupting the equilibrium.[25]In pure substances (C = 1), the rule implies exactly one triple point for any specific set of three phases, as the invariance pins down a unique (T, P) coordinate where their chemical potentials balance.[26] However, if the substance exhibits more than three phases—such as due to polymorphic solid forms—multiple triple points can exist, each corresponding to a distinct triplet of phases and appearing as separate invariant loci in the phase diagram.[27] For instance, metals like iron display multiple such points owing to their polymorphic transitions under varying pressure.[27]The rule extends to multicomponent systems (C > 1), where three-phase coexistence yields F = C - 1 \geq 1, allowing variability along lines (univariant for C = 2) or surfaces (divariant for C = 3) in the appropriate thermodynamic space, rather than isolated points.[25] These "generalized triple points" thus form extended manifolds, enabling phase transitions to occur over ranges of conditions influenced by composition.[24]The Gibbs phase rule presupposes thermodynamic equilibrium and ignores external influences such as gravitational or magnetic fields, which could introduce additional variables or alter phase boundaries in non-ideal scenarios.[28] In phase diagrams, these invariant points manifest as intersections of phase boundaries, directly resulting from the rule's constraints.[29]
Triple Point of Water
Gas-Liquid-Solid Triple Point
The gas-liquid-solid triple point of water occurs at a precisely defined temperature of 273.16 K (0.01 °C) and a pressure of 611.657 Pa (approximately 0.006 atm), where the three phases—ice Ih (hexagonal ice), liquid water, and water vapor—coexist in thermodynamic equilibrium.[30][5] At this point, the system is invariant, with no degrees of freedom, meaning any change in temperature or pressure would disrupt the phase balance.[6]In this equilibrium state, the liquid phase exhibits its minimum vapor pressure, equal to the saturation pressure of both the solid and vapor phases, ensuring all three coexist without net phase transition.[30] The ice Ih phase has a lower density than the liquid (approximately 0.917 g/cm³ versus 0.9998 g/cm³ at the triple point), which influences the phase boundaries.[6] While slight supercooling of the liquid below 273.16 K is possible under certain conditions, the equilibrium at the triple point remains stable once achieved, as the phases mutually sustain each other.[31]This triple point holds critical significance in temperature metrology, serving as the primary fixed point for the International Temperature Scale of 1990 (ITS-90), where it anchors the Kelvin scale at exactly 273.16 K by definition.[32][33] Even following the 2019 SI redefinition of the kelvin, which fixed the Boltzmann constant, the water triple point continues to provide a practical realization for high-precision temperature measurements across the ITS-90 range from 0.65 K to 1357.77 K.[33]Water's triple point is unique due to its anomalous density behavior: unlike most substances, liquid water reaches maximum density at approximately 4 °C, leading to a negative slope in the solid-liquid phaseboundary on the pressure-temperature diagram.[21] This anomaly arises because the molar volume change upon melting (ΔV_melting > 0) results from ice Ih's open crystal structure, causing the melting point to decrease with increasing pressure and positioning the triple point at a low but positive pressure.[21][34]
Triple Points with High-Pressure Ice Phases
Water exhibits a remarkably complex phase behavior under elevated pressures, manifesting in over 20 known crystalline polymorphs of ice beyond the familiar ice Ih, including notable high-pressure phases such as ice II, III, V, VI, and VII. These polymorphs arise due to the versatile hydrogen-bonding network of water molecules, which rearranges into diverse structures stabilized at pressures ranging from hundreds of megapascals to gigapascals. Each additional ice phase introduces new equilibrium lines in the phase diagram, leading to a proliferation of triple points where three phases coexist stably. The Gibbs phase rule, with its variance of one for a single-component system like water, permits these multiple triple points as distinct polymorphs emerge with changing pressure and temperature.[35] Recent discoveries as of 2025, such as Ice XXI, continue to expand this list.[36]Prominent examples of triple points involving high-pressure ice phases highlight this intricacy. The triple point where ice Ih, liquid water, and ice III coexist occurs at approximately 251 K and 210 MPa, marking the boundary beyond which ice III becomes the stable solid phase under compression.[37] Similarly, the triple point between ice V, ice VI, and liquid water is located at about 273.3 K and 632 MPa, delineating the transition to denser, more symmetric ice structures prevalent at deeper geophysical conditions.[38] These points, determined through experimental and computational methods, underscore the negative pressure dependence of water's melting curve for these phases, where increasing pressure lowers the melting temperature relative to ambient conditions.The abundance of such triple points delineates the multifaceted phase diagram of water, essential for understanding phenomena in high-pressure environments like the interiors of icy planets, subduction zones in Earth's mantle, and exoplanetary oceans. For instance, phases like ice VI and VII dominate under pressures exceeding 1 GPa, influencing the thermal and structural evolution of celestial bodies such as Uranus and Neptune.[39] This complexity arises from the competition between entropy and density-driven stabilization, resulting in reentrant melting behaviors where liquid water can reappear at extreme pressures.Recent investigations, particularly post-2020, have refined the phase diagram by confirming additional triple points associated with proton-ordered phases like ice XV and XVI. For example, computational studies predict a triple point among ice XIV, XV, and VIII at 1.258 GPa and 112 K, validating the stability of these low-temperature, high-pressure polymorphs up to about 1 GPa.[40] These findings, derived from ab initio simulations, extend the known boundaries of ice polymorphism and highlight ongoing discoveries in water's high-pressure behavior, with implications for modeling planetary geophysics and materials under extreme conditions.[41]
Measurement and Metrological Applications
Triple-Point Cells
Triple-point cells are precision-engineered devices designed to realize and maintain the triple point of a pure substance, enabling accurate temperature measurements in metrology. These cells consist of sealed containers filled with the substance, allowing the coexistence of solid, liquid, and vapor phases in thermodynamic equilibrium. They are essential for primary thermometry, particularly for substances like water and gallium, where the triple point provides a reproducible fixed temperature.[5]The construction of triple-point cells typically involves a sealed glass or metal enclosure to contain the pure substance under controlled conditions. For water triple-point cells, borosilicate or fused-silica glass cylinders are commonly used, with a central well for inserting thermometers and re-entrant tubes to facilitate phase manipulation. These cells are partially filled with the substance, leaving space for vapor, and are hermetically sealed to prevent contamination or pressure loss. Metal cells, such as those for gallium, employ quartz or metal alloys for the body to handle higher temperatures, often with an outer mantle or jacket for uniform thermal control during operation. The mantle, typically a surrounding bath or insulating layer, helps maintain isothermal conditions and prevents external influences from disrupting the equilibrium.[42][43]Materials selection emphasizes high purity to ensure the triple point temperature remains unshifted by impurities, which can depress the equilibriumtemperature. For water cells, the sample must exceed 99.9999% purity, with an isotopic composition closely matching Vienna Standard Mean Ocean Water (VSMOW) to achieve uncertainties below 0.1 mK; deviations in deuterium or oxygen-18 content can alter the triple point by up to several millikelvins. Gallium cells require similar ultra-high purity (>99.99999%) to minimize supercooling or impurity effects. International standards are established through comparisons at institutions like NIST and BIPM, where reference cells are certified and deviations between national standards are tracked to within 0.05 mK.[44][45][46]In operation, the cell is first fully frozen by immersing it in a cooling mixture, such as dry ice and alcohol, to form a solid mantle around the thermometer well. It is then inverted and gently heated from the base—often via a stirred waterbath or electrical heater in the mantle—to partially melt the solid, establishing the triple-point plateau where solid, liquid, and vapor coexist stably. This plateau temperature, for water at 273.16 K, is measured directly with a thermometer inserted into the well. The internal vapor pressure, fixed at the triple point (approximately 611 Pa for water), can be verified using a connected manometer to confirm equilibrium, though routine use focuses on the thermal plateau for calibration. The process ensures a stable environment lasting hours to days, with the cell maintained in a temperature-controlled bath near the triple point to prevent phase shifts.[42][5][47]The development of water triple-point cells began in the 1950s at the National Bureau of Standards (now NIST), where early sealed designs enabled practical realization of the equilibrium for thermometry. These innovations evolved through the 1960s with improvements in sealing and purity control, becoming integral to international temperature scales. By the late 20th century, such cells had become the standard for primary thermometry, with ongoing refinements in isotopic control and construction enhancing accuracy to microkelvin levels.[43]
Role in Temperature Standards
The International Temperature Scale of 1990 (ITS-90) relies on triple points as primary defining fixed points to establish a practical temperature scale closely approximating thermodynamic temperature. These include the triple points of hydrogen at 13.8033 K, neon at 24.5561 K, oxygen at 54.3584 K, argon at 83.8058 K, mercury at 234.3156 K, and water at 273.16 K, among others, which serve as anchors for calibration across various temperature ranges.[48] Triple-point cells enable the precise realization of these points, allowing thermometers to be calibrated directly against the coexistence equilibrium of the three phases.A key advantage of triple points in temperature standards is their exceptional reproducibility, typically achieving uncertainties as low as 0.1 mK, due to the invariant temperature and pressure at which the solid, liquid, and gas phases coexist without needing external pressure measurements.[49] This independence from pressure gauges enhances reliability in metrology, making triple points superior to vapor-pressure or boiling points for defining fixed temperatures. In the calibration process, for instance, an interpolating constant-volume hydrogen or helium gas thermometer is calibrated against multiple triple points, such as those of equilibrium hydrogen, neon, and e-H₂ vapor pressure points, to define temperatures between 3 K and 24.5561 K.The 2019 redefinition of the International System of Units (SI) fixed the Boltzmann constant, rendering the triple point of water a measured value approximately 273.16 K rather than exactly defining the kelvin, yet ITS-90 continues to use these triple points as operational anchors for practical temperature realization.[5] This maintains continuity in metrology while allowing for improved accuracy through ongoing refinements in fixed-point realizations. As of 2024, investigations are underway to replace the mercury triple point due to toxicity concerns, with alternatives such as the triple points of carbon dioxide and xenon being evaluated for better reproducibility and safety.[50] Concurrently, research into quantum-based alternatives, such as Johnson noise thermometry, explores primary thermometry methods that could eventually supplement or replace traditional triple-point calibrations by directly linking to fundamental constants.[51][52]
Triple Points of Selected Substances
Examples from Common Elements and Compounds
The triple point of carbon dioxide occurs at a temperature of 216.58 K and a pressure of 5.185 bar (equivalent to approximately 5.11 atm).[53] This elevated pressure relative to atmospheric conditions means that solidcarbon dioxide, commonly known as dry ice, sublimes directly to gas at standard pressure without passing through a liquidphase, a behavior that distinguishes it from substances like water.[54] The coexistence of solid, liquid, and gaseous phases at this point highlights the role of intermolecular forces in phase stability for molecular solids under compression.Unlike most substances, helium-4 lacks a conventional gas-liquid-solid triple point due to the absence of a stablesolid-gas equilibrium at low pressures; solidhelium-4 requires pressures exceeding about 2.5 MPa to form, preventing the intersection of solid, liquid, and vapor phases in the phase diagram.[55] Instead, helium-4 exhibits a lambda transition at 2.17 K under its saturated vapor pressure, marking the onset of superfluidity in the liquid phase, where viscosity vanishes and unique quantum behaviors emerge.[56] Metastable extensions of phase boundaries have been studied experimentally, revealing potential solid-liquid-gas coexistence under specific non-equilibrium conditions, but these do not constitute a stable triple point.[57]Mercury's triple point is realized at 234.3 K and an extremely low pressure of 1.65 × 10^{-7} kPa, reflecting the weak van der Waals intermolecular forces that allow the solid and liquid phases to coexist with vapor only under near-vacuum conditions.[58] This low pressure underscores mercury's tendency to vaporize readily, contributing to its historical use in thermometers while posing toxicity risks, and the triple point serves as a fixed reference in low-temperature metrology despite not being a primary standard.[59]For ammonia, the triple point lies at 195.49 K and 6.060 kPa (0.060 bar), a condition where solid, liquid, and gas phases equilibrate, enabling its application in refrigeration cycles that exploit phase changes near atmospheric pressure.[60] The relatively low temperature and modest pressure facilitate efficient heat absorption during evaporation, making ammonia a key refrigerant in industrial systems, though its corrosiveness limits broader use.[61]Sulfur's phase behavior is complicated by its allotropes, resulting in multiple triple points; for instance, the rhombic-monoclinic-vapor triple point occurs at approximately 368.6 K and a low pressure of about 5 × 10^{-6} bar, while the rhombic-liquid-vapor triple point is at 388.4 K and 2.3 × 10^{-5} bar.[62] These points arise from the polymorphic nature of solid sulfur, with rhombic (α-sulfur) as the stable low-temperature form transitioning to monoclinic (β-sulfur) upon heating, and recent assessments confirm the persistence of these equilibria under low-pressure conditions, influencing sulfur's industrial processing and volcanic emissions.[63] High-pressure studies up to 65 GPa reveal additional allotropic transitions, but the low-pressure triple points dominate ambient applications.[64]Benzene, as a representative organic compound, has a triple point at 278.5 K and 4.79 kPa, where the solid, liquid, and vapor phases coexist, close to its normal melting point of 278.7 K at atmospheric pressure due to the compound's relatively high vapor pressure.[65] This proximity allows benzene to melt without significant pressure adjustment, and the triple point data inform thermodynamic models for aromatic hydrocarbons in petrochemical processes.[66] Recent equations of state extend these properties to high pressures up to 1800 MPa, aiding simulations of molecular crystals under compression.[67]
Comprehensive Table of Triple Points
The following table compiles triple point data for selected substances, drawn from authoritative sources such as the NIST Chemistry WebBook. These values represent the equilibrium conditions for the solid, liquid, and gas phases unless otherwise noted for allotropes or special cases. Temperatures are given in kelvin (K) and degrees Celsius (°C), pressures in pascals (Pa) and atmospheres (atm), with notes on uncertainties and sources where applicable.
This compilation highlights trends across substance classes, such as the increasing triple point temperature and pressure with atomic or molecular mass among noble gases (e.g., from Ne at 24.6 K, 0.43 atm to Xe at 161.4 K, 0.81 atm), reflecting stronger intermolecular forces. For metals, triple points occur at higher temperatures but extremely low pressures due to low vapor pressures of the liquids. Data are based on 2023-updated NIST sources, ensuring consistency with experimental measurements.