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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]
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 ...
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 ...
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.
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]
Fractionation makes it possible to isolate more than two components in a mixture in a single run. This property sets it apart from other separation techniques. Fractionation is widely employed in many branches of science and technology. Mixtures of liquids and gasses are separated by fractional distillation by difference in boiling point.
Stable isotopes do not decay, and the heavy and light isotope masses affect how they partition within the environment. Any deviation from a random distribution of the light and heavy isotopes within the environment is called fractionation, and consistent fractionations as a result of a particular process or reaction are called "isotope effects."
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 ...