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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 ...
Since its original descriptions, the Urey–Bigeleisen–Mayer equation has taken many forms. Given an isotopic exchange reaction + = +, such that designates a molecule containing an isotope of interest, the equation can be expressed by relating the equilibrium constant, , to the product of partition function ratios, namely the translational, rotational, vibrational, and sometimes electronic ...
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]
A primary kinetic isotope effect (PKIE) may be found when a bond to the isotopically labeled atom is being formed or broken. [3] [4]: 427 Depending on the way a KIE is probed (parallel measurement of rates vs. intermolecular competition vs. intramolecular competition), the observation of a PKIE is indicative of breaking/forming a bond to the isotope at the rate-limiting step, or subsequent ...
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]
The equations can be used to describe an isotope fractionation process if: (1) material is continuously removed from a mixed system containing molecules of two or more isotopic species (e.g., water with 18 O and 16 O, or sulfate with 34 S and 32 S), (2) the fractionation accompanying the removal process at any instance is described by the ...
Isotope geochemistry is an aspect of geology based upon the study of natural variations in the relative abundances of isotopes of various elements. Variations in isotopic abundance are measured by isotope-ratio mass spectrometry , and can reveal information about the ages and origins of rock, air or water bodies, or processes of mixing between ...