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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 degrees of freedom, is the number of components and is the number of phases, then :F = C - P + 2 It was derived by American physicist Josiah Willard Gibbs in his landmark paper titled ''On the Equilibrium of Heterogeneous Substances'', published in parts between 1875 and 1878. The rule assumes the components do not react with each other. The number of degrees of freedom is the number of independent intensive variables, i.e. the largest number of thermodynamic parameters such as temperature or pressure that can be varied simultaneously and arbitrarily without determining one another. An example of one-component system is a system involving one pure chemical, while two-component systems, such as mixtures of water and ethanol, have two chem ...
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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 thermodynamics which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology. Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines, particularly through the work of French physicist Sadi Carnot (1824) who believed that engine efficiency was the key that could help France win the Napoleonic Wars. Scots-Irish physicist Lord Kelvin was the first to formula ...
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Liquid
A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, and plasma), and is the only state with a definite volume but no fixed shape. A liquid is made up of tiny vibrating particles of matter, such as atoms, held together by intermolecular bonds. Like a gas, a liquid is able to flow and take the shape of a container. Most liquids resist compression, although others can be compressed. Unlike a gas, a liquid does not disperse to fill every space of a container, and maintains a fairly constant density. A distinctive property of the liquid state is surface tension, leading to wetting phenomena. Water is by far the most common liquid on Earth. The density of a liquid is usually close to that of a solid, and much higher than that of a gas. Therefore, liquid and solid are both termed condensed mat ...
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Ice III
Ice III is a form of solid matter which consists of tetragonal crystalline ice, formed by cooling water down to at . It is the least dense of the high-pressure water phases, with a density of (at 350 MPa). It has a very high relative permittivity at 117 and has a density of (making it more dense than water). The proton-ordered form of is ice IX. Ordinary water ice is known as , (in the Bridgman nomenclature). Different types of ice, from Ice II to Ice XIX Ice XIX is a proposed crystalline phase of water. Along with ice XV, it is one of two phases of ice directly related to ice VI. Ice XIX is prepared by cooling HCl-doped ice VI at a pressure above 1.6 GPa down to about 100 K. As of 2022, its cry ..., have been created in the laboratory at different temperatures and pressures. See also * Ice, for other crystalline forms of ice References * Water ice {{inorganic-compound-stub ...
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Ice I
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-phase-one) is the hexagonal crystal form of ordinary ice, or frozen water. Virtually all ice in the biosphere is ice Ih, with the exception only of a small amount of ice Ic that is occasionally present in the upper atmosphere. Ice Ih exhibits many peculiar properties that are relevant to the existence of life and regulation of global climate. For a description of these properties, see '' Ice'', which deals primarily with ice Ih. The crystal structure is characterized by the oxygen atoms forming hexagonal symmetry with near tetrahedral bonding angles. Ice Ih is stable down to , as evidenced by x-ray diffraction and extremely high resolution thermal expansion measurements. Ice Ih is also stable under applied pressures of up to about wher ...
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Triple Point
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.. It is that temperature and pressure at which the sublimation curve, fusion 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 triple point of water was used to define the kelvin, 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. The triple points ...
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Melting Point
The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends on pressure and is usually specified at a standard pressure such as 1 atmosphere or 100 kPa. When considered as the temperature of the reverse change from liquid to solid, it is referred to as the freezing point or crystallization point. Because of the ability of substances to supercool, the freezing point can easily appear to be below its actual value. When the "characteristic freezing point" of a substance is determined, in fact, the actual methodology is almost always "the principle of observing the disappearance rather than the formation of ice, that is, the melting point." Examples For most substances, melting and freezing points are approximately equal. For example, the melting point ''and'' freezing point of mercury ...
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Supercritical Fluid
A supercritical fluid (SCF) is any substance at a temperature and pressure above its critical point (chemistry), critical point, where distinct liquid and gas phases do not exist, but below the pressure required to compress it into a solid. It can Effusion, effuse through porous solids like a gas, overcoming the mass transfer limitations that slow liquid transport through such materials. SCF are much superior to gases in their ability to Solvation, dissolve materials like liquids or solids. Also, near the critical point, small changes in pressure or temperature result in large changes in density, allowing many properties of a supercritical fluid to be "fine-tuned". Supercritical fluids occur in the atmospheres of the gas giants Jupiter and Saturn, the terrestrial planet Venus, and probably in those of the ice giants Uranus and Neptune. Supercritical water is found on Earth, such as the water issuing from black smokers, a type of underwater hydrothermal vent. They are used as a sub ...
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Critical Point (thermodynamics)
In thermodynamics, a critical point (or critical state) is the end point of a phase equilibrium curve. The most prominent 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 cannot be liquefied by pressure alone. At the critical point, defined by a ''critical temperature'' ''T''c and a ''critical pressure'' ''p''c, phase boundaries vanish. Other examples include the liquid–liquid critical points in mixtures, and the ferromagnet–paramagnet transition ( Curie temperature) in the absence of an external magnetic field. Liquid–vapor critical point Overview For simplicity and clarity, the generic notion of ''critical point'' is best introduced by discussing a specific example, the vapor–liquid critical point. This was the first critical point to be discovered, and it is still the best known and most studied one. The fi ...
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Phase Diagram
A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions (pressure, temperature, volume, etc.) at which thermodynamically distinct phases (such as solid, liquid or gaseous states) occur and coexist at equilibrium. Overview Common components of a phase diagram are ''lines of equilibrium'' or ''phase boundaries'', which refer to lines that mark conditions under which multiple phases can coexist at equilibrium. Phase transitions occur along lines of equilibrium. Metastable phases are not shown in phase diagrams as, despite their common occurrence, they are not equilibrium phases. Triple points are points on phase diagrams where lines of equilibrium intersect. Triple points mark conditions at which three different phases can coexist. For example, the water phase diagram has a triple point corresponding to the single temperature and pressure at which solid, liquid, and gaseous water can coexist in a stab ...
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Carbon Dioxide Pressure-temperature Phase Diagram
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon makes up only about 0.025 percent of Earth's crust. Three isotopes occur naturally, C and C being stable, while C is a radionuclide, decaying with a half-life of about 5,730 years. Carbon is one of the few elements known since antiquity. Carbon is the 15th most abundant element in the Earth's crust, and the fourth most abundant element in the universe by mass after hydrogen, helium, and oxygen. Carbon's abundance, its unique diversity of organic compounds, and its unusual ability to form polymers at the temperatures commonly encountered on Earth, enables this element to serve as a common element of all known life. It is the second most abundant element in the human body by mass (about 18.5%) after oxygen. The atoms of carbon can bond ...
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Chemical Potential
In thermodynamics, the chemical potential of a species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potential of a species in a mixture is defined as the rate of change of free energy of a thermodynamic system with respect to the change in the number of atoms or molecules of the species that are added to the system. Thus, it is the partial derivative of the free energy with respect to the amount of the species, all other species' concentrations in the mixture remaining constant. When both temperature and pressure are held constant, and the number of particles is expressed in moles, the chemical potential is the partial molar Gibbs free energy. At chemical equilibrium or in phase equilibrium, the total sum of the product of chemical potentials and stoichiometric coefficients is zero, as the free energy is at a minimum. In a system in diffusion equilibrium, ...
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Miscibility
Miscibility () is the property of two substances to mix in all proportions (that is, to fully dissolve in each other at any concentration), forming a homogeneous mixture (a solution). The term is most often applied to liquids but also applies to solids and gases. For example, water and ethanol are miscible because they mix in all proportions. By contrast, substances are said to be immiscible if there are certain proportions in which the mixture does not form a solution. For one example, oil is not soluble in water, so these two solvents are immiscible. As another example, butanone (methyl ethyl ketone) is significantly soluble in water, but these two solvents are also immiscible because in some proportions the mixture will separate into two phases. Organic compounds In organic compounds, the weight percent of hydrocarbon chain often determines the compound's miscibility with water. For example, among the alcohols, ethanol has two carbon atoms and is miscible with wat ...
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