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Entropy Of Activation
In chemical kinetics, the entropy of activation of a reaction is one of the two parameters (along with the enthalpy of activation) which are typically obtained from the temperature dependence of a reaction rate constant, when these data are analyzed using the Eyring equation of the transition state theory. The standard entropy of activation is symbolized and equals the change in entropy when the reactants change from their initial state to the activated complex or transition state ( = change, = entropy, = activation). It determines the preexponential factor of the Arrhenius equation for temperature dependence of reaction rates. The relationship depends on the molecularity of the reaction: for reactions in solution and unimolecular gas reactions , while for bimolecular gas reactions . In these equations is the base of natural logarithms, is the Planck constant, is the Boltzmann constant and the absolute temperature. ' is the ideal gas constant in units of (bar·L)/(mol·K). T ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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), ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Natural Logarithm
The natural logarithm of a number is its logarithm to the base of the mathematical constant , which is an irrational and transcendental number approximately equal to . The natural logarithm of is generally written as , , or sometimes, if the base is implicit, simply . Parentheses are sometimes added for clarity, giving , , or . This is done particularly when the argument to the logarithm is not a single symbol, so as to prevent ambiguity. The natural logarithm of is the power to which would have to be raised to equal . For example, is , because . The natural logarithm of itself, , is , because , while the natural logarithm of is , since . The natural logarithm can be defined for any positive real number as the area under the curve from to (with the area being negative when ). The simplicity of this definition, which is matched in many other formulas involving the natural logarithm, leads to the term "natural". The definition of the natural logarithm can the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Dissociative Substitution
In chemistry, dissociative substitution describes a Chemical reaction, reaction pathway by which Chemical compound, compounds interchange ligands. The term is typically applied to Coordination chemistry, coordination and Organometallic chemistry, organometallic complexes, but resembles the SN1 reaction, SN1 mechanism in organic chemistry. This pathway can be well described by the cis effect, ''cis'' effect, or the labilization of CO ligands in the ''cis'' position. The opposite pathway is associative substitution, being analogous to SN2 reaction, SN2 pathway. Pathways that are intermediate between the pure dissociative and pure associative pathways are called interchange mechanisms. Complexes that undergo dissociative substitution are often coordinative unsaturation, coordinatively saturated and often have octahedral molecular geometry. The entropy of activation is characteristically positive for these reactions, which indicates that the disorder of the reacting system increases ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Rate Determining Step
In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS or RD-step or r/d step) or rate-limiting step. For a given reaction mechanism, the prediction of the corresponding rate equation (for comparison with the experimental rate law) is often simplified by using this approximation of the rate-determining step. In principle, the time evolution of the reactant and product concentrations can be determined from the set of simultaneous rate equations for the individual steps of the mechanism, one for each step. However, the analytical solution of these differential equations is not always easy, and in some cases numerical integration may even be required. The hypothesis of a single rate-determining step can greatly simplify the mathematics. In the simplest case the initial step is the slowest, and the overall rate is just the rate of the first step. Also, the rate equations for mechanisms with a s ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Keith J
Keith may refer to: People and fictional characters * Keith (given name), includes a list of people and fictional characters * Keith (surname) * Keith (singer), American singer James Keefer (born 1949) * Baron Keith, a line of Scottish barons in the late 18th century * Clan Keith, a Scottish clan associated with lands in northeastern and northwestern Scotland Places Australia * Keith, South Australia, a town and locality Scotland * Keith, Moray, a town ** Keith railway station * Keith Marischal, East Lothian United States * Keith, Georgia, an unincorporated community * Keith, Ohio, an unincorporated community * Keith, West Virginia, an unincorporated community * Keith, Wisconsin, a ghost town * Keith County, Nebraska Other uses * Keith F.C., a football team based in Keith, Scotland * , a ship of the British Royal Navy * Hurricane Keith, a 2000 hurricane that caused extensive damage in Central America * ''Keith'' (film), a 2008 independent film directed by Todd Kessle ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Absolute Temperature
Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic work and heat transfer as defined in thermodynamics, but the kelvin was redefined by international agreement in 2019 in terms of phenomena that are now understood as manifestations of the kinetic energy of free motion of microscopic particles such as atoms, molecules, and electrons. From the thermodynamic viewpoint, for historical reasons, because of how it is defined and measured, this microscopic kinetic definition is regarded as an "empirical" temperature. It was adopted because in practice it can generally be measured more precisely than can Kelvin's thermodynamic temperature. A thermodynamic temperature reading of zero is of particular importance for the third law of thermodynamics. By convention, it is reported on the '' Kelvin scale ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Boltzmann Constant
The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constant, and in Planck's law of black-body radiation and Boltzmann's entropy formula, and is used in calculating thermal noise in resistors. The Boltzmann constant has dimensions of energy divided by temperature, the same as entropy. It is named after the Austrian scientist Ludwig Boltzmann. As part of the 2019 redefinition of SI base units, the Boltzmann constant is one of the seven " defining constants" that have been given exact definitions. They are used in various combinations to define the seven SI base units. The Boltzmann constant is defined to be exactly . Roles of the Boltzmann constant Macroscopically, the ideal gas law states that, for an ideal gas, the product of pressure and volume is proportional to the product of amount ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Planck Constant
The Planck constant, or Planck's constant, is a fundamental physical constant of foundational importance in quantum mechanics. The constant gives the relationship between the energy of a photon and its frequency, and by the mass-energy equivalence, the relationship between mass and frequency. Specifically, a photon's energy is equal to its frequency multiplied by the Planck constant. The constant is generally denoted by h. The reduced Planck constant, or Dirac constant, equal to the constant divided by 2 \pi, is denoted by \hbar. In metrology it is used, together with other constants, to define the kilogram, the SI unit of mass. The SI units are defined in such a way that, when the Planck constant is expressed in SI units, it has the exact value The constant was first postulated by Max Planck in 1900 as part of a solution to the ultraviolet catastrophe. At the end of the 19th century, accurate measurements of the spectrum of black body radiation existed, but the distr ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molecularity
In chemistry, molecularity is the number of molecules that come together to react in an elementary (single-step) reactionAtkins, P.; de Paula, J. Physical Chemistry. Oxford University Press, 2014 and is equal to the sum of stoichiometric coefficients of reactants in the elementary reaction with effective collision ( sufficient energy) and correct orientation. Depending on how many molecules come together, a reaction can be unimolecular, bimolecular or even trimolecular. The kinetic order of any elementary reaction or reaction step is ''equal'' to its molecularity, and the rate equation of an elementary reaction can therefore be determined by inspection, from the molecularity. The kinetic order of a complex (multistep) reaction, however, is not necessarily equal to the number of molecules involved. The concept of molecularity is only useful to describe elementary reactions or steps. Unimolecular reactions In a unimolecular reaction, a single molecule rearranges atoms, forming ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Arrhenius Equation
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. Laidler, K. J. (1987) ''Chemical Kinetics'', Third Edition, Harper & Row, p. 42 Currently, it is best seen as an empirical relationship.Kenneth Connors, Chemical Kinetics, 1990, VCH Publishers It can be used to model the temperature variation of diffusion coefficients, population of crystal vacancies, creep rates, and many other thermally-induced processes ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Preexponential Factor
In chemical kinetics, the pre-exponential factor or A factor is the pre-exponential constant in the Arrhenius equation (equation shown below), an empirical relationship between temperature and 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 units of s−1. For that reason, it is often called ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
