Steric Factor
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Steric Factor
The steric factor, usually denoted ''ρ'', is a quantity used in collision theory. Also called the ''probability factor'', the steric factor is defined as the ratio between the experimental value of the rate constant and the one predicted by collision theory. It can also be defined as the ratio between the pre-exponential factor and the collision frequency, and it is most often less than unity. Physically, the steric factor can be interpreted as the ratio of the cross section for reactive collisions to the total collision cross section. Usually, the more complex the reactant molecules, the lower the steric factors. Nevertheless, some reactions exhibit steric factors greater than unity: the harpoon reactions, which involve atoms that exchange electrons, producing ions. The deviation from unity can have different causes: the molecules are not spherical, so different geometries are possible; not all the kinetic energy is delivered into the right spot; the presence of a solvent (wh ...
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Collision Theory
Collision theory is a principle of chemistry used to predict the rates of chemical reactions. It states that when suitable particles of the reactant hit each other with correct orientation, only a certain amount of collisions result in a perceptible or notable change; these successful changes are called successful collisions. The successful collisions must have enough energy, also known as activation energy, at the moment of impact to break the pre-existing bonds and form all new bonds. This results in the products of the reaction. Increasing the concentration of the reactant brings about more collisions and hence more successful collisions. Increasing the temperature increases the average kinetic energy of the molecules in a solution, increasing the number of collisions that have enough energy. Collision theory was proposed independently by Max Trautz in 1916 and William Lewis in 1918. When a catalyst is involved in the collision between the reactant molecules, less energy is ...
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Rate Constant
In chemical kinetics a reaction rate constant or reaction rate coefficient, ''k'', quantifies the rate and direction of a chemical reaction. For a reaction between reactants A and B to form product C the reaction rate is often found to have the form: r = k(T) mathrmm mathrm Here ''k''(''T'') is the reaction rate constant that depends on temperature, and and 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 solution. (For a reaction taking place at a boundary, one would use moles of A or B per unit area instead.) The exponents ''m'' and ''n'' are called partial orders of reaction and are ''not'' generally equal to the stoichiometric coefficients ''a'' and ''b''. Instead they depend on the reaction mechanism and can be determined experimentally. Elementary steps For an elementary step, there ''is'' a relationship between stoichiometry and rate law, as determined by the ...
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Pre-exponential Factor
In chemical kinetics, the pre-exponential factor or A factor is the pre-exponential constant in the Arrhenius equation#Equation, Arrhenius equation (equation shown below), an empirical relationship between temperature and Reaction rate constant, rate coefficient. It is usually designated by A when determined from experiment, while Z is usually left for collision frequency. The pre-exponential factor can be thought of as a measure of the frequency of properly oriented collisions. It is typically determined experimentally by measuring the rate constant k at a particular temperature and fitting the data to the Arrhenius equation. The pre-exponential factor is generally not exactly constant, but rather depends on the specific reaction being studied and the temperature at which the reaction is occurring. A=\frac The units of the pre-exponential factor A are identical to those of the rate constant and will vary depending on the order of the reaction. For a first-order reaction, it has ...
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Collision Frequency
Collision frequency describes the rate of collisions between two atomic or molecular species in a given volume, per unit time. In an ideal gas, assuming that the species behave like hard spheres, the collision frequency between entities of species A and species B is: : Z = N_\text N_\text \sigma_\text \sqrt\frac, SI unit of ''Z'' is the volumetric collision rate (unit m3⋅s−1). where: * N_\text is the number of A molecules in the gas, * N_\text is the number of B molecules in the gas, * \sigma_\text is the collision cross section (unit m2), the area when two molecules collide with each other, simplified to \sigma_\text = \pi(r_\text+r_\text)^2 , where r_\text the radius of A and r_\text the radius of B. * k_\text is the Boltzmann constant (unit m2⋅kg⋅s−2⋅K−1), * T is the temperature (unit K), * \mu_\text is the reduced mass of the reactants A and B, \mu_\text = \frac (unit kg) Collision in diluted solution Collision in diluted gas or liquid solution i ...
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Cross Section (physics)
In physics, the cross section is a measure of the probability that a specific process will take place when some kind of radiant excitation (e.g. a particle beam, sound wave, light, or an X-ray) intersects a localized phenomenon (e.g. a particle or density fluctuation). For example, the Rutherford cross-section is a measure of probability that an alpha particle will be deflected by a given angle during an interaction with an atomic nucleus. Cross section is typically denoted ( sigma) and is expressed in units of area, more specifically in barns. In a way, it can be thought of as the size of the object that the excitation must hit in order for the process to occur, but more exactly, it is a parameter of a stochastic process. In classical physics, this probability often converges to a deterministic proportion of excitation energy involved in the process, so that, for example, with light scattering off of a particle, the cross section specifies the amount of optical power scattere ...
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Molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and biochemistry, the distinction from ions is dropped and ''molecule'' is often used when referring to polyatomic ions. A molecule may be homonuclear, that is, it consists of atoms of one chemical element, e.g. two atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of more than one element, e.g. water (two hydrogen atoms and one oxygen atom; H2O). In the kinetic theory of gases, the term ''molecule'' is often used for any gaseous particle regardless of its composition. This relaxes the requirement that a molecule contains two or more atoms, since the noble gases are individual atoms. Atoms and complexes connected by non-covalent interactions, such as hydrogen bonds or ionic bonds, are typically not consid ...
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Harpoon Reaction
A harpoon reaction is a type of chemical reaction, first proposed by Michael Polanyi in 1920, whose mechanism (also called the harpooning mechanism) involves two neutral reactants undergoing an electron transfer over a relatively long distance to form ions that then attract each other closer together. For example, a metal atom and a halogen might react to form a cation and anion, respectively, leading to a combined metal halide. The main feature of these redox reactions is that, unlike most reactions, they have steric factors greater than unity; that is, they take place faster than predicted by collision theory. This is explained by the fact that the colliding particles have greater cross sections than the pure geometrical ones calculated from their radii, because when the particles are close enough, an electron "jumps" (therefore the name) from one of the particles to the other one, forming an anion and a cation which subsequently attract each other. Harpoon reactions usually tak ...
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Kinetic Energy
In physics, the kinetic energy of an object is the energy that it possesses due to its motion. It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acceleration, the body maintains this kinetic energy unless its speed changes. The same amount of work is done by the body when decelerating from its current speed to a state of rest. Formally, a kinetic energy is any term in a system's Lagrangian which includes a derivative with respect to time. In classical mechanics, the kinetic energy of a non-rotating object of mass ''m'' traveling at a speed ''v'' is \fracmv^2. In relativistic mechanics, this is a good approximation only when ''v'' is much less than the speed of light. The standard unit of kinetic energy is the joule, while the English unit of kinetic energy is the foot-pound. History and etymology The adjective ''kinetic'' has its roots in the Greek word κίνησις ''kinesis'', m ...
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Solvent
A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for polar molecules and the most common solvent used by living things; all the ions and proteins in a cell are dissolved in water within the cell. The quantity of solute that can dissolve in a specific volume of solvent varies with temperature. Major uses of solvents are in paints, paint removers, inks, and dry cleaning. Specific uses for organic solvents are in dry cleaning (e.g. tetrachloroethylene); as paint thinners (toluene, turpentine); as nail polish removers and solvents of glue (acetone, methyl acetate, ethyl acetate); in spot removers (hexane, petrol ether); in detergents ( citrus terpenes); and in perfumes (ethanol). Solvents find various applications in chemical, pharmaceutical, oil, and gas industries, including in chemical syn ...
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Solvent Cage
In chemistry, the cage effect (also known as geminate recombination) describes how the properties of a molecule are affected by its surroundings. First introduced by Franck and Rabinowitch in 1934, the cage effect suggests that instead of acting as an individual particle, molecules in solvent are more accurately described as an encapsulated particle. The encapsulated molecules or radicals are called cage pairs or geminate pairs. In order to interact with other molecules, the caged particle must diffuse from its solvent cage. The typical lifetime of a solvent cage is 10 seconds. Many manifestations of the cage effect exist. In free radical polymerization, radicals formed from the decomposition of an initiator molecule are surrounded by a cage consisting of solvent and/or monomer molecules. Within the cage, the free radicals undergo many collisions leading to their recombination or mutual deactivation. This can be described by the following reaction: : R\!-\!R \;\;\underse ...
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Chemical Kinetics
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 to be contrasted with 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. History In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating the law of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances.C.M. Guldberg and P. Waage,"Studies Concerning Affinity" ''Forhandlinger i Videnskabs-Selskabet i Christiania'' (1864), 35P. W ...
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