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Edwards Equation
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 (relative to protons) and its polarizability. This equation was first developed by John O. Edwards in 1954 and later revised based on additional work in 1956. The general idea is that most nucleophiles are also good bases because the concentration of negatively charged electron density that defines a nucleophile will strongly attract positively charged protons, which is the definition of a base according to Brønsted–Lowry acid-base theory. Additionally, highly polarizable nucleophiles will have greater nucleophilic character than suggested by their basicity because their electron density can be shifted with relative ease to concentrate in one area. History Prior to Edwards developing his equation, other scientists were also working to define nucleophilicity quantitatively. Brønsted and Pede ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nucleophile
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases. ''Nucleophilic'' describes the affinity of a nucleophile to bond with positively charged Atomic nucleus, atomic nuclei. Nucleophilicity, sometimes referred to as nucleophile strength, refers to a substance's nucleophilic character and is often used to compare the affinity of atoms. Neutral nucleophilic reactions with solvents such as Alcohol (chemistry), alcohols and water are named solvolysis. Nucleophiles may take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial positive charge, and nucleophilic addition. Nucleophilicity is closely related to basicity. The difference between the two is, that basicity is a thermodynamic property (i.e. relates to an equilibrium state), but nucleop ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Base (chemistry)
In chemistry, there are three definitions in common use of the word "base": '' Arrhenius bases'', '' Brønsted bases'', and '' Lewis bases''. All definitions agree that bases are substances that react with acid An acid is a molecule or ion capable of either donating a proton (i.e. Hydron, hydrogen cation, H+), known as a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis ...s, as originally proposed by Guillaume-François Rouelle, G.-F. Rouelle in the mid-18th century. In 1884, Svante Arrhenius proposed that a base is a substance which dissociates in aqueous solution to form hydroxide ions OH−. These ions can react with Hydron (chemistry), hydrogen ions (H+ according to Arrhenius) from the dissociation of acids to form water in an acid–base reaction. A base was therefore a metal hydroxide such as NaOH or Calcium hydroxide, Ca(OH)2. Such aqueous hydroxide solutions were also described by ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Polarizability
Polarizability usually refers to the tendency of matter, when subjected to an electric field, to acquire an electric dipole moment in proportion to that applied field. It is a property of particles with an electric charge. When subject to an electric field, the negatively charged electrons and positively charged atomic nuclei are subject to opposite forces and undergo Electric dipole moment, charge separation. Polarizability is responsible for a material's dielectric constant and, at high (optical) frequencies, its refractive index. The polarizability of an atom or molecule is defined as the ratio of its induced dipole moment to the local electric field; in a crystalline solid, one considers the dipole moment per unit cell. Note that the local electric field seen by a molecule is generally different from the macroscopic electric field that would be measured externally. This discrepancy is taken into account by the Clausius–Mossotti relation (below) which connects the bulk behavi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Electron Density
Electron density or electronic density is the measure of the probability of an electron being present at an infinitesimal element of space surrounding any given point. It is a scalar quantity depending upon three spatial variables and is typically denoted as either \rho(\textbf r) or n(\textbf r). The density is determined, through definition, by the normalised N-electron wavefunction which itself depends upon 4N variables (3N spatial and N Spin (physics), spin coordinates). Conversely, the density determines the wave function modulo up to a phase factor, providing the formal foundation of density functional theory. According to quantum mechanics, due to the uncertainty principle on an atomic scale the exact location of an electron cannot be predicted, only the probability of its being at a given position; therefore electrons in atoms and molecules act as if they are "smeared out" in space. For one-electron systems, the electron density at any point is proportional to the square ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Nucleophilicity
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are Lewis bases. ''Nucleophilic'' describes the affinity of a nucleophile to bond with positively charged atomic nuclei. Nucleophilicity, sometimes referred to as nucleophile strength, refers to a substance's nucleophilic character and is often used to compare the affinity of atoms. Neutral nucleophilic reactions with solvents such as alcohols and water are named solvolysis. Nucleophiles may take part in nucleophilic substitution, whereby a nucleophile becomes attracted to a full or partial positive charge, and nucleophilic addition. Nucleophilicity is closely related to basicity. The difference between the two is, that basicity is a thermodynamic property (i.e. relates to an equilibrium state), but nucleophilicity is a kinetic property, whic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Methyl Bromide
Bromomethane, commonly known as methyl bromide, is an organobromine compound with chemical formula, formula Carbon, CHydrogen, H3Bromine, Br. This colorless, odorless, nonflammable gas is Bromine cycle, produced both industrially and biologically. It is a recognized ozone depletion, ozone-depleting chemical. According to the IPCC Fifth Assessment Report, it has a Global warming potential, global warming potential of 2. The compound was used extensively as a pesticide until being phased out by most countries in the early 2000s. From a chemistry perspective, it is one of the halomethanes. Occurrence and manufacture Marine organisms are estimated to produce 56,000 tonnes annually. It is also produced in small quantities by certain terrestrial plants, such as members of the family Brassicaceae. In 2009, an estimated 24,000 tonnes of methyl bromide were produced. Its production was curtailed by the Montreal Protocol, such that in 1983, production was nearly twice that of 2009 level ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hammett Equation
In organic chemistry, the Hammett equation describes a linear free-energy relationship relating reaction rates and equilibrium constants for many reactions involving benzoic acid derivatives with meta- and para-substituents to each other with just two parameters: a substituent constant and a reaction constant. This equation was developed and published by Louis Plack Hammett in 1937 as a follow-up to qualitative observations in his 1935 publication. The basic idea is that for any two reactions with two aromatic reactants only differing in the type of substituent, the change in free energy of activation is proportional to the change in Gibbs free energy. This notion does not follow from elemental thermochemistry or chemical kinetics and was introduced by Hammett intuitively. The basic equation is: :\log \frac = \sigma\rho where :_0 = Reference constant :\sigma = Substituent constant :\rho = Reaction rate constant relating the equilibrium constant, , for a given equilibrium ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molar Refractivity
Molar refractivity, R_m, is a measure of the total polarizability of a mole of a substance. For a perfect dielectric which is made of one type of molecule, the molar refractivity is proportional to the polarizability of a single molecule of the substance. For real materials, intermolecular interactions (the effect of the induced dipole moment of one molecule on the field felt by nearby molecules) give rise to a density dependence. The molar refractivity is commonly expressed as a sum of components, where the leading order is the value for a perfect dielectric, followed by the density-dependent corrections: : R_m = A + B\cdot\rho + C\cdot\rho^2 + ... The coefficients A, B, C, ... are called the refractivity virial coefficients. Some research papers are dedicated to finding the values of the subleading coefficients of different substances. In other contexts, the material can be assumed to be approximately perfect, so that the only coefficient of interest is A . The coefficien ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Alpha Effect
The alpha effect refers to the increased Nucleophile, nucleophilicity of an atom due to the presence of an adjacent (alpha) atom with lone pair electrons. This first atom does not necessarily exhibit increased basicity compared with a similar atom without an adjacent electron-donating atom, resulting in a deviation from the classical Brønsted-type reactivity-basicity relationship. In other words, the alpha effect refers to nucleophiles presenting higher nucleophilicity than the predicted value obtained from the Brønsted basicity. The representative examples would be high nucleophilicities of hydroperoxide (HO2−) and hydrazine (N2H4). The effect is now well established with numerous examples and became an important concept in mechanistic chemistry and biochemistry. However, the origin of the effect is still controversial without a clear winner. Background Experiment The effect was first observed by Jencks and Carriuolo in 1960 in a series of chemical kinetics experiments in ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
HSAB Theory
HSAB is an acronym for "hard and soft (Lewis) acids and bases". HSAB is widely used in chemistry for explaining the stability of compounds, reaction mechanisms and pathways. It assigns the terms 'hard' or 'soft', and 'acid' or 'base' to chemical species. 'Hard' applies to species which are small, have high charge states (the charge criterion applies mainly to acids, to a lesser extent to bases), and are weakly polarizable. 'Soft' applies to species which are big, have low charge states and are strongly polarizable. The theory is used in contexts where a qualitative, rather than quantitative, description would help in understanding the predominant factors which drive chemical properties and reactions. This is especially so in transition metal chemistry, where numerous experiments have been done to determine the relative ordering of ligands and transition metal ions in terms of their hardness and softness. HSAB theory is also useful in predicting the products of metathesis react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Free-energy Relationship
In physical organic chemistry, a free-energy relationship or Gibbs energy relation relates the logarithm of a reaction rate constant or equilibrium constant for one series of chemical reactions with the logarithm of the rate or equilibrium constant for a related series of reactions. Free energy relationships establish the extent at which bond formation and breakage happen in the transition state of a reaction, and in combination with kinetic isotope experiments a reaction mechanism can be determined. Free energy relationships are often used to calculate equilibrium constants since they are experimentally difficult to determine. The most common form of free-energy relationships are linear free-energy relationships (LFER). The Brønsted catalysis equation describes the relationship between the ionization constant of a series of catalysts and the reaction rate constant for a reaction on which the catalyst operates. The Hammett equation predicts the equilibrium constant or react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
