Equilibrium Fractionation
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Equilibrium Fractionation
Equilibrium isotope fractionation is the partial separation of isotopes between two or more substances in chemical equilibrium. Equilibrium fractionation is strongest at low temperatures, and (along with kinetic isotope effects) forms the basis of the most widely used isotopic paleothermometers (or climate proxies): D/H and 18O/16O records from ice cores, and 18O/16O records from calcium carbonate. It is thus important for the construction of geologic temperature records. Isotopic fractionations attributed to equilibrium processes have been observed in many elements, from hydrogen ( D/H) to uranium ( 238U/235U). In general, the light elements (especially hydrogen, boron, carbon, nitrogen, oxygen and sulfur) are most susceptible to fractionation, and their isotopes tend to be separated to a greater degree than heavier elements. Definition Most equilibrium fractionations are thought to result from the reduction in vibrational energy (especially zero-point energy) when a more mass ...
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Isotope Fractionation
Isotope fractionation describes fractionation processes that affect the relative abundance of isotopes, phenomena which are taken advantage of in isotope geochemistry and other fields. Normally, the focus is on stable isotopes of the same element. Isotopic fractionation can be measured by isotope analysis, using isotope-ratio mass spectrometry or cavity ring-down spectroscopy to measure ratios of isotopes, an important tool to understand geochemical and biological systems. For example, biochemical processes cause changes in ratios of stable carbon isotopes incorporated into biomass. Definition Stable isotopes partitioning between two substances ''A'' and ''B'' can be expressed by the use of the isotopic fractionation factor (alpha): where ''R'' is the ratio of the heavy to light isotope (e.g., 2H/1H or 18O/16O). Values for alpha tend to be very close to 1. McGlynn, Shawn E.; "Biological Isotope Fractionation and Earth History: From Enzymes to Cells to Ecosystems" pp 59-79 in ...
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Zero-point Energy
Zero-point energy (ZPE) is the lowest possible energy that a quantum mechanical system may have. Unlike in classical mechanics, quantum systems constantly Quantum fluctuation, fluctuate in their lowest energy state as described by the Heisenberg uncertainty principle. Therefore, even at absolute zero, atoms and molecules retain some vibrational motion. Apart from atoms and molecules, the empty space of Vacuum state, the vacuum also has these properties. According to quantum field theory, the universe can be thought of not as isolated particles but continuous fluctuating Field (physics), fields: matter fields, whose Quantum, quanta are fermions (i.e., leptons and quarks), and Force field (physics), force fields, whose quanta are bosons (e.g., photons and gluons). All these fields have zero-point energy. These fluctuating zero-point fields lead to a kind of reintroduction of an Luminiferous aether, aether in physics since some systems can detect the existence of this energy. ...
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Equilibrium Constant
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at equilibrium. However, reaction parameters like temperature, solvent, and ionic strength may all influence the value of the equilibrium constant. A knowledge of equilibrium constants is essential for the understanding of many chemical systems, as well as biochemical processes such as oxygen transport by hemoglobin in blood and acid–base homeostasis in the human body. Stability constants, formation cons ...
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Transient Kinetic Isotope Fractionation
Transient kinetic isotope effects (or fractionation) occur when the Chemical reaction, reaction leading to isotope fractionation does not follow pure First order kinetics, first-order kinetics and therefore isotopic effects cannot be described with the classical equilibrium fractionation equations or with steady-state Kinetic isotope effect, kinetic fractionation equations (also known as the Rayleigh equation). In these instances, the general equations for biochemical isotope kinetics (GEBIK) and the general equations for biochemical isotope fractionation (GEBIF) can be used. The GEBIK and GEBIF equations are the most generalized approach to describe isotopic effects in any Chemical reaction, chemical, Chemical reaction#Catalysis, catalytic reaction and Chemical reaction#Biochemical reactions, biochemical reactions because they can describe isotopic effects in equilibrium reactions, kinetic chemical reactions and kinetic biochemical reactions. In the latter two cases, they can de ...
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Mass-independent Fractionation
Mass-independent isotope fractionation or Non-mass-dependent fractionation (NMD), refers to any chemical or physical process that acts to separate isotopes, where the amount of separation does not scale in proportion with the difference in the masses of the isotopes. Most isotopic fractionations (including typical kinetic fractionations and equilibrium fractionations) are caused by the effects of the mass of an isotope on atomic or molecular velocities, diffusivities or bond strengths. Mass-independent fractionation processes are less common, occurring mainly in photochemical and spin-forbidden reactions. Observation of mass-independently fractionated materials can therefore be used to trace these types of reactions in nature and in laboratory experiments. Mass-independent fractionation in nature The most notable examples of mass-independent fractionation in nature are found in the isotopes of oxygen and sulfur. The first example was discovered by Robert N. Clayton, Toshiko Mayeda ...
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Kinetic Fractionation
Kinetic fractionation is an isotopic fractionation process that separates stable isotopes from each other by their mass during unidirectional processes. Biological processes are generally unidirectional and are very good examples of "kinetic" isotope reactions. All organisms preferentially use lighter isotopic species, because "energy costs" are lower, resulting in a significant fractionation between the substrate (heavier) and the biologically mediated product (lighter). As an example, photosynthesis preferentially takes up the light isotope of carbon 12C during assimilation of an atmospheric CO2 molecule. This kinetic isotope fractionation explains why plant material (and thus fossil fuels, which are derived from plants) is typically depleted in 13C by 25 per mil (2.5 per cent) relative to most inorganic carbon on Earth. A naturally occurring example of non-biological kinetic fractionation occurs during the evaporation of seawater to form clouds under conditions in which some par ...
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Transient Kinetic Isotope Fractionation
Transient kinetic isotope effects (or fractionation) occur when the Chemical reaction, reaction leading to isotope fractionation does not follow pure First order kinetics, first-order kinetics and therefore isotopic effects cannot be described with the classical equilibrium fractionation equations or with steady-state Kinetic isotope effect, kinetic fractionation equations (also known as the Rayleigh equation). In these instances, the general equations for biochemical isotope kinetics (GEBIK) and the general equations for biochemical isotope fractionation (GEBIF) can be used. The GEBIK and GEBIF equations are the most generalized approach to describe isotopic effects in any Chemical reaction, chemical, Chemical reaction#Catalysis, catalytic reaction and Chemical reaction#Biochemical reactions, biochemical reactions because they can describe isotopic effects in equilibrium reactions, kinetic chemical reactions and kinetic biochemical reactions. In the latter two cases, they can de ...
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Non-equilibrium
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities (non-equilibrium state variables) that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of chemical reactions. Almost all systems found in nature are not in thermodynamic equilibrium, for they are changing or can be triggered to change over time, and are continuously and discontinuously subject to flux of matter and energy to and from other systems and to chemical reactions. Some systems and processes are, however, in a useful sense, near enough to thermodynamic equilibrium to allow description with useful accuracy by currently known non-equilibrium thermodynamics. Nevertheless, many natural systems and processes will always remain far beyond the scope o ...
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Mass-independent Fractionation
Mass-independent isotope fractionation or Non-mass-dependent fractionation (NMD), refers to any chemical or physical process that acts to separate isotopes, where the amount of separation does not scale in proportion with the difference in the masses of the isotopes. Most isotopic fractionations (including typical kinetic fractionations and equilibrium fractionations) are caused by the effects of the mass of an isotope on atomic or molecular velocities, diffusivities or bond strengths. Mass-independent fractionation processes are less common, occurring mainly in photochemical and spin-forbidden reactions. Observation of mass-independently fractionated materials can therefore be used to trace these types of reactions in nature and in laboratory experiments. Mass-independent fractionation in nature The most notable examples of mass-independent fractionation in nature are found in the isotopes of oxygen and sulfur. The first example was discovered by Robert N. Clayton, Toshiko Mayeda ...
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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 phase of water. It is one state of water within the hydrosphere. Water vapor can be produced from the evaporation or boiling of liquid water or from the sublimation of ice. Water vapor is transparent, like most constituents of the atmosphere. Under typical atmospheric conditions, water vapor is continuously generated by evaporation and removed by condensation. It is less dense than most of the other constituents of air and triggers convection currents that can lead to clouds. Being a component of Earth's hydrosphere and hydrologic cycle, it is particularly abundant in Earth's atmosphere, where it acts as a greenhouse gas and warming feedback, contributing more to total greenhouse effect than non-condensable gases such as carbon dioxide an ...
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Water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a solvent). It is vital for all known forms of life, despite not providing food, energy or organic micronutrients. Its chemical formula, H2O, indicates that each of its molecules contains one oxygen and two hydrogen atoms, connected by covalent bonds. The hydrogen atoms are attached to the oxygen atom at an angle of 104.45°. "Water" is also the name of the liquid state of H2O at standard temperature and pressure. A number of natural states of water exist. It forms precipitation in the form of rain and aerosols in the form of fog. Clouds consist of suspended droplets of water and ice, its solid state. When finely divided, crystalline ice may precipitate in the form of snow. The gaseous state of water is steam or water vapor. Water co ...
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Rotational Symmetry
Rotational symmetry, also known as radial symmetry in geometry, is the property a shape has when it looks the same after some rotation by a partial turn. An object's degree of rotational symmetry is the number of distinct orientations in which it looks exactly the same for each rotation. Certain geometric objects are partially symmetrical when rotated at certain angles such as squares rotated 90°, however the only geometric objects that are fully rotationally symmetric at any angle are spheres, circles and other spheroids. Formal treatment Formally the rotational symmetry is symmetry with respect to some or all rotations in ''m''-dimensional Euclidean space. Rotations are direct isometries, i.e., isometries preserving orientation. Therefore, a symmetry group of rotational symmetry is a subgroup of ''E''+(''m'') (see Euclidean group). Symmetry with respect to all rotations about all points implies translational symmetry with respect to all translations, so space is homo ...
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