The Swain equation relates the kinetic isotope effect for the protium/tritium combination with that of the protium/deuterium combination according to:
where kH,D,T are the reaction rate constants for the protonated, deuterated and tritiated reactants respectively.
Bessel functions, first defined by the mathematician Daniel Bernoulli and then generalized by Friedrich Bessel, are canonical solutions y(x) of Bessel's differential equation for an arbitrary complex number , which represents the order of the Bessel function. Although and produce the same differential equation, it is conventional to define different Bessel functions for these two values in such a way that the Bessel functions are mostly smooth functions of .
Deuterium (hydrogen-2, symbol 2H or D, also known as heavy hydrogen) is one of two stable isotopes of hydrogen; the other is protium, or hydrogen-1, 1H. The deuterium nucleus, called a deuteron, contains one proton and one neutron, whereas the far more common 1H has no neutrons. Deuterium has a natural abundance in Earth's oceans of about one atom of deuterium in every 6,420 atoms of hydrogen. Thus deuterium accounts for about 0.0156% by number (0.0312% by mass) of all hydrogen in the ocean: 4.85×1013 tonnes of deuterium – mainly as HOD (or 1HO2H or 1H2HO) and only rarely as D2O (or 2H2O) – in 1.4×1018 tonnes of water. The abundance of 2H changes slightly from one kind of natural water to another (see Vienna Standard Mean Ocean Water).
A hydrogen atom is an atom of the chemical element hydrogen. The electrically neutral hydrogen atom contains a nucleus of a single positively charged proton and a single negatively charged electron bound to the nucleus by the Coulomb force. Atomic hydrogen constitutes about 75% of the baryonic mass of the universe.
The Schrödinger equation is a partial differential equation that governs the wave function of a quantum-mechanical system. Its discovery was a significant landmark in the development of quantum mechanics. It is named after Erwin Schrödinger, who postulated the equation in 1925 and published it in 1926, forming the basis for the work that resulted in his Nobel Prize in Physics in 1933.
The ideal gas law, also called the general gas equation, is the equation of state of a hypothetical ideal gas. It is a good approximation of the behavior of many gases under many conditions, although it has several limitations. It was first stated by Benoît Paul Émile Clapeyron in 1834 as a combination of the empirical Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. The ideal gas law is often written in an empirical form:
In mathematics and physics, the heat equation is a certain partial differential equation. Solutions of the heat equation are sometimes known as caloric functions. The theory of the heat equation was first developed by Joseph Fourier in 1822 for the purpose of modeling how a quantity such as heat diffuses through a given region.
In physics, Hamiltonian mechanics is a reformulation of Lagrangian mechanics that emerged in 1833. Introduced by Sir William Rowan Hamilton, Hamiltonian mechanics replaces (generalized) velocities used in Lagrangian mechanics with (generalized) momenta. Both theories provide interpretations of classical mechanics and describe the same physical phenomena.
In numerical analysis, the Runge–Kutta methods are a family of implicit and explicit iterative methods, which include the Euler method, used in temporal discretization for the approximate solutions of simultaneous nonlinear equations. These methods were developed around 1900 by the German mathematicians Carl Runge and Wilhelm Kutta.
In mathematics, an eigenfunction of a linear operator D defined on some function space is any non-zero function in that space that, when acted upon by D, is only multiplied by some scaling factor called an eigenvalue. As an equation, this condition can be written as for some scalar eigenvalue The solutions to this equation may also be subject to boundary conditions that limit the allowable eigenvalues and eigenfunctions.
The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit time. Reaction rates can vary dramatically. For example, the oxidative rusting of iron under Earth's atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second. For most reactions, the rate decreases as the reaction proceeds. A reaction's rate can be determined by measuring the changes in concentration over time.
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. Formally, it is the ratio of rate constants for the reactions involving the light (kL) and the heavy (kH) isotopically substituted reactants (isotopologues): KIE = kL/kH.
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at equilibrium. However, reaction parameters like temperature, solvent, and ionic strength may all influence the value of the equilibrium constant.
The Friedmann equations, also known as the Friedmann–Lemaître (FL) equations, are a set of equations in physical cosmology that govern the expansion of space in homogeneous and isotropic models of the universe within the context of general relativity. They were first derived by Alexander Friedmann in 1922 from Einstein's field equations of gravitation for the Friedmann–Lemaître–Robertson–Walker metric and a perfect fluid with a given mass density ρ and pressure p. The equations for negative spatial curvature were given by Friedmann in 1924.
In mathematics, the Helmholtz equation is the eigenvalue problem for the Laplace operator. It corresponds to the elliptic partial differential equation: where ∇2 is the Laplace operator, k2 is the eigenvalue, and f is the (eigen)function. When the equation is applied to waves, k is known as the wave number. The Helmholtz equation has a variety of applications in physics and other sciences, including the wave equation, the diffusion equation, and the Schrödinger equation for a free particle.
Diffusion is the net movement of anything generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical potential. It is possible to diffuse "uphill" from a region of lower concentration to a region of higher concentration, as in spinodal decomposition. Diffusion is a stochastic process due to the inherent randomness of the diffusing entity and can be used to model many real-life stochastic scenarios. Therefore, diffusion and the corresponding mathematical models are used in several fields beyond physics, such as statistics, probability theory, information theory, neural networks, finance, and marketing.
In physics, Lagrangian mechanics is a formulation of classical mechanics founded on the stationary-action principle. It was introduced by the Italian-French mathematician and astronomer Joseph-Louis Lagrange in his presentation to the Turin Academy of Science in 1760 culminating in his 1788 grand opus, Mécanique analytique.
Transient kinetic isotope effects 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. In these instances, the general equations for biochemical isotope kinetics (GEBIK) and the general equations for biochemical isotope fractionation (GEBIF) can be used.
The Edwards equation in organic chemistry is a two-parameter equation for correlating nucleophilic reactivity, as defined by relative rate constants, with the basicity of the nucleophile and its polarizability. This equation was first developed by John O. Edwards in 1954 and later revised based on additional work in 1956.
In nuclear physics, the Bateman equation is a mathematical model describing abundances and activities in a decay chain as a function of time, based on the decay rates and initial abundances. The model was formulated by Ernest Rutherford in 1905 and the analytical solution was provided by Harry Bateman in 1910.
Methane clumped isotopes are methane molecules that contain two or more rare isotopes. Methane (CH4) contains two elements, carbon and hydrogen, each of which has two stable isotopes. For carbon, 98.9% are in the form of carbon-12 (12C) and 1.1% are carbon-13 (13C); while for hydrogen, 99.99% are in the form of protium (1H) and 0.01% are deuterium (2H or D). Carbon-13 (13C) and deuterium (2H or D) are rare isotopes in methane molecules. The abundance of the clumped isotopes provides information independent from the traditional carbon or hydrogen isotope composition of methane molecules.
