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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 ...
where A and B are reactants C is a product a, b, and c are stoichiometric coefficients,. the reaction rate is often found to have the form: = [] [] Here is the reaction rate constant that depends on temperature, and [A] and [B] are the molar concentrations of substances A and B in moles per unit volume of solution, assuming the reaction is taking place throughout the volume of the ...
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]
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 ...
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 ...
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).
A common form for the rate equation is a power law: [6] = [] [] The constant is called the rate constant.The exponents, which can be fractional, [6] are called partial orders of reaction and their sum is the overall order of reaction.
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]