A side reaction is a chemical reaction that occurs at the same time as the actual main reaction, but to a lesser extent. It leads to the formation of by-product, so that the yield of main product is reduced: [1]
P1 is the main product if k1> k2. The by-product P2 is generally undesirable and must be separated from the actual main product (usually in a costly process).
B and C from the above equations usually represent different compounds. However, they could also just be different positions in the same molecule.
A side reaction is also referred to as competing reaction [2] [3] when different compounds (B, C) compete for another reactant (A). If the side reaction occurs about as often as the main reaction, it is spoken of parallel reactions [4] (especially in the kinetics, see below).
Also there may be more complicated relationships: Compound A could reversibly but quickly react to substance B (with speed k1) or irreversible but slow (k1> k−1 >> k2) to substance C:
Assuming that the reaction to substance C is irreversible, as it is thermodynamically very stable. In this case, B is the kinetic and C is the thermodynamic product of the reaction (see also here). [5] [6] [7] If the reaction is carried out at low temperatures and stopped after a short time, it is spoken of kinetic control, primarily the kinetic product B would be formed. When the reaction is carried out at high temperatures and for long time (in which case the necessary activation energy for the reaction to C is available, which is progressively formed over time), it is spoken of thermodynamic control; the thermodynamic product C is primarily formed.
In organic synthesis, elevated temperatures usually lead to more side products. Side products are usually undesirable, therefore low temperatures are preferred ("mild conditions"). The ratio between competing reactions may be influenced by a change in temperature because their activation energies are different in most cases. Reactions with high activation energy can be more strongly accelerated by an increase in temperature than those with low activation energy. Also, the state of equilibrium depends on temperature. [8]
Detection reactions can be distorted by side reactions.
Side reactions are also described in the reaction kinetics, a branch of physical chemistry. Side reactions are understood as complex reaction, since the overall reaction (main reaction + side reaction) is composed of several (at least two) elementary reactions. [9] Other complex reactions are competing reactions, parallel reactions, consecutive reactions, chain reactions, reversible reactions, etc. [10] [10] : 280–291
If one reaction occurs much faster than the other one (k1 > k2), it (k1) will be called the main reaction, the other one (k2) side reaction. If both reactions roughly of same speed (k1 ≅ k2) is spoken of parallel reactions. [4]
If the reactions and are irreversibly (without reverse reaction), then the ratio of P1 and P2 corresponds to the relative reactivity of B and C compared with A:
In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the system. This state results when the forward reaction proceeds at the same rate as the reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium.
A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the nuclei, and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive elements where both electronic and nuclear changes can occur.
In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (Ea) of a reaction is measured in joules per mole (J/mol), kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol). Activation energy can be thought of as the magnitude of the potential barrier (sometimes called the energy barrier) separating minima of the potential energy surface pertaining to the initial and final thermodynamic state. For a chemical reaction to proceed at a reasonable rate, the temperature of the system should be high enough such that there exists an appreciable number of molecules with translational energy equal to or greater than the activation energy. The term "activation energy" was introduced in 1889 by the Swedish scientist Svante Arrhenius.
In physical chemistry, the Arrhenius equation is a formula for the temperature dependence of reaction rates. The equation was proposed by Svante Arrhenius in 1889, based on the work of Dutch chemist Jacobus Henricus van 't Hoff who had noted in 1884 that the van 't Hoff equation for the temperature dependence of equilibrium constants suggests such a formula for the rates of both forward and reverse reactions. This equation has a vast and important application in determining the rate of chemical reactions and for calculation of energy of activation. Arrhenius provided a physical justification and interpretation for the formula. Currently, it is best seen as an empirical relationship. It can be used to model the temperature variation of diffusion coefficients, population of crystal vacancies, creep rates, and many other thermally-induced processes/reactions. The Eyring equation, developed in 1935, also expresses the relationship between rate and energy.
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.
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is different from chemical thermodynamics, which deals with the direction in which a reaction occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction.
In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical reaction occurs.
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):
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.
Thermodynamic reaction control or kinetic reaction control in a chemical reaction can decide the composition in a reaction product mixture when competing pathways lead to different products and the reaction conditions influence the selectivity or stereoselectivity. The distinction is relevant when product A forms faster than product B because the activation energy for product A is lower than that for product B, yet product B is more stable. In such a case A is the kinetic product and is favoured under kinetic control and B is the thermodynamic product and is favoured under thermodynamic control.
In organic chemistry, cheletropic reactions, also known as chelotropic reactions, are a type of pericyclic reaction. Specifically, cheletropic reactions are a subclass of cycloadditions. The key distinguishing feature of cheletropic reactions is that on one of the reagents, both new bonds are being made to the same atom.
The principle of detailed balance can be used in kinetic systems which are decomposed into elementary processes. It states that at equilibrium, each elementary process is in equilibrium with its reverse process.
The Curtin–Hammett principle is a principle in chemical kinetics proposed by David Yarrow Curtin and Louis Plack Hammett. It states that, for a reaction that has a pair of reactive intermediates or reactants that interconvert rapidly, each going irreversibly to a different product, the product ratio will depend both on the difference in energy between the two conformers and the energy barriers from each of the rapidly equilibrating isomers to their respective products. Stated another way, the product distribution reflects the difference in energy between the two rate-limiting transition states. As a result, the product distribution will not necessarily reflect the equilibrium distribution of the two intermediates. The Curtin–Hammett principle has been invoked to explain selectivity in a variety of stereo- and regioselective reactions. The relationship between the (apparent) rate constants and equilibrium constant is known as the Winstein-Holness equation.
In chemistry, transition state theory (TST) explains the reaction rates of elementary chemical reactions. The theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and activated transition state complexes.
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 forms the basis of the most widely used isotopic paleothermometers : D/H and 18O/16O records from ice cores, and 18O/16O records from calcium carbonate. It is thus important for the construction of geologic temperature records. Isotopic fractionations attributed to equilibrium processes have been observed in many elements, from hydrogen (D/H) to uranium (238U/235U). In general, the light elements are most susceptible to fractionation, and their isotopes tend to be separated to a greater degree than heavier elements.
In theoretical chemistry, an energy profile is a theoretical representation of a chemical reaction or process as a single energetic pathway as the reactants are transformed into products. This pathway runs along the reaction coordinate, which is a parametric curve that follows the pathway of the reaction and indicates its progress; thus, energy profiles are also called reaction coordinate diagrams. They are derived from the corresponding potential energy surface (PES), which is used in computational chemistry to model chemical reactions by relating the energy of a molecule(s) to its structure.
Unimolecular ion decomposition is the fragmentation of a gas phase ion in a reaction with a molecularity of one. Ions with sufficient internal energy may fragment in a mass spectrometer, which in some cases may degrade the mass spectrometer performance, but in other cases, such as tandem mass spectrometry, the fragmentation can reveal information about the structure of the ion.
Transient kinetic isotope effects occur when the reaction leading to isotope fractionation does not follow pure first-order kinetics 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 magnetocrystalline anisotropy energy of a ferromagnetic crystal can be expressed as a power series of direction cosines of the magnetic moment with respect to the crystal axes. The coefficient of those terms is the constant anisotropy. In general, the expansion is limited to a few terms. Normally the magnetization curve is continuous with respect to the applied field up to saturation but, in certain intervals of the anisotropy constant values, irreversible field-induced rotations of the magnetization are possible, implying first-order magnetization transition between equivalent magnetization minima, the so-called first-order magnetization process (FOMP).
Shape control in nanocrystal growth is the control of the shape of nanocrystals formed in their synthesis by means of varying reaction conditions. This is a concept studied in nanosciences, which is a part of both chemistry and condensed matter physics. There are two processes involved in the growth of these nanocrystals. Firstly, volume Gibbs free energy of the system containing the nanocrystal in solution decreases as the nanocrystal size increases. Secondly, each crystal has a surface Gibbs free energy that can be minimized by adopting the shape that is energetically most favorable. Surface energies of crystal planes are related to their Miller indices, which is why these can help predict the equilibrium shape of a certain nanocrystal.
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