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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 ...
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Isotope Fractionation
Isotope fractionation describes fractionation processes that affect the relative abundance of isotopes, a phenomena that occurs (and so advantage is taken of it) in the study geochemistry, biochemistry, food science, 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, nuclear magnetic resonance methods ( specialised techniques,) cavity ring-down spectroscopy, etc., to measure ratios of isotopes, important tools to understand geochemical and biological systems, past and present. 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 v ...
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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. How ...
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Isotope Analysis
Isotope analysis is the identification of isotopic signature, abundance of certain stable isotopes of chemical elements within organic and inorganic compounds. Isotopic analysis can be used to understand the flow of energy through a food web, to reconstruct past environmental and climatic conditions, to investigate human and animal diets, for food authentification, and a variety of other physical, geological, palaeontological and chemical processes. Stable isotope ratios are measured using mass spectrometry, which separates the different isotopes of an element on the basis of their mass-to-charge ratio. Tissues affected Isotopic oxygen is incorporated into the body primarily through ingestion at which point it is used in the formation of, for archaeological purposes, bones and teeth. The oxygen is incorporated into the hydroxylcarbonic apatite of bone and tooth enamel. Bone is continually remodelled throughout the lifetime of an individual. Although the rate of tur ...
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Transient Kinetic Isotope Fractionation
Transient kinetic isotope effects (or fractionation) occur when the reaction leading to isotope fractionation does not follow pure first-order kinetics (FOK) and therefore isotopic effects cannot be described with the classical equilibrium fractionation equations or with steady-state 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, catalytic reaction and 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 describe both stationary and non-stationary fractionation (i.e., variable and inverse fractionation). In general, isotopic effects depend on the num ...
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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 May ...
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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 isotopes, because "energy costs" are lower, resulting in a significant fractionation between the substrate (heavier) and the biologically mediated product (lighter). For example, photosynthesis preferentially takes up the light isotope of carbon C during assimilation of atmospheric CO. This kinetic isotope fractionation explains why plant material (and thus fossil fuels, which are derived from plants) is typically depleted in C by 25 per mil (2.5%) 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 part of the transport is unidirection ...
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Transient Kinetic Isotope Fractionation
Transient kinetic isotope effects (or fractionation) occur when the reaction leading to isotope fractionation does not follow pure first-order kinetics (FOK) and therefore isotopic effects cannot be described with the classical equilibrium fractionation equations or with steady-state 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, catalytic reaction and 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 describe both stationary and non-stationary fractionation (i.e., variable and inverse fractionation). In general, isotopic effects depend on the num ...
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Non-equilibrium Thermodynamics
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. Many systems and processes can, however, be considered to be in equilibrium locally, thus allowing description by currently known equilibrium thermodynamics. Nevertheless, some natural systems and processes remain beyond the scope of equilibrium thermodynamic methods due to the exis ...
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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 May ...
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Water Vapor
Water vapor, water vapour, or aqueous vapor is the gaseous phase of Properties of water, water. It is one Phase (matter), state of water within the hydrosphere. Water vapor can be produced from the evaporation or boiling of liquid water or from the Sublimation (phase transition), 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 and fog. 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 and methane. Use of water vapor, as steam, has been important for cooking, and as a major component in energy prod ...
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Water
Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It 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, , 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°. In liquid form, is also called "water" at standard temperature and pressure. Because Earth's environment is relatively close to water's triple point, water exists on Earth as a solid, a liquid, and a gas. 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 ...
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Rotational Symmetry
Rotational symmetry, also known as radial symmetry in geometry, is the property a shape (geometry), shape has when it looks the same after some rotation (mathematics), rotation by a partial turn (angle), turn. An object's degree of rotational symmetry is the number of distinct Orientation (geometry), 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 -dimensional Euclidean space. Rotations are Euclidean group#Direct and indirect isometries, direct isometries, i.e., Isometry, isometries preserving Orientation (mathematics), orientation. Therefore, a symmetry group of rotational symmetry is a subgroup of (see Euclidean g ...
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