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Initially used to approximate chemical reaction rates, [7] [8] models of isotope fractionation are used throughout the physical sciences. In chemistry , the Urey–Bigeleisen–Mayer equation has been used to predict equilibrium isotope effects and interpret the distributions of isotopes and isotopologues within systems, especially as ...
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 18 O/ 16 O records from ice cores, and 18 O/ 16 O records from calcium ...
Isotope fractionation occurs during a phase transition, when the ratio of light to heavy isotopes in the involved molecules changes. When water vapor condenses (an equilibrium fractionation), the heavier water isotopes (18 O and 2 H) become enriched in the liquid phase while the lighter isotopes (16 O and 1 H) tend toward the vapor phase. [1]
In chemistry, the rate equation (also known as the rate law or empirical differential rate equation) is an empirical differential mathematical expression for the reaction rate of a given reaction in terms of concentrations of chemical species and constant parameters (normally rate coefficients and partial orders of reaction) only. [1]
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). [1]
In physical organic chemistry, a kinetic isotope effect (KIE) is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. [3] Formally, it is the ratio of rate constants for the reactions involving the light ( k L ) and the heavy ( k H ) isotopically substituted reactants ...
Denitrification can lead to a condition called isotopic fractionation in the soil environment. The two stable isotopes of nitrogen, 14 N and 15 N are both found in the sediment profiles. The lighter isotope of nitrogen, 14 N, is preferred during denitrification, leaving the heavier nitrogen isotope, 15 N, in the residual matter.
Nitrogen-15 is a rare stable isotope of nitrogen. Two sources of nitrogen-15 are the positron emission of oxygen-15 [8] and the beta decay of carbon-15. Nitrogen-15 presents one of the lowest thermal neutron capture cross sections of all isotopes. [9] Nitrogen-15 is frequently used in NMR (Nitrogen-15 NMR spectroscopy).