Associative Pathway
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Associative Pathway
Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to organometallic and coordination complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to the Sn1 pathway. Intermediate pathways exist between the pure associative and pure dissociative pathways, these are called interchange mechanisms. Associative pathways are characterized by binding of the attacking nucleophile to give a discrete, detectable intermediate followed by loss of another ligand. Complexes that undergo associative substitution are either coordinatively unsaturated or contain a ligand that can change its bonding to the metal, e.g. change in hapticity or bending of a nitrogen oxide ligand (NO). In homogeneous catalysis, the associative pathway is desirable because the binding event, and hence the selectivity of the reaction, depends not only on the nature of the meta ...
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Chemical Compound
A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element is therefore not a compound. A compound can be transformed into a different substance by a chemical reaction, which may involve interactions with other substances. In this process, bonds between atoms may be broken and/or new bonds formed. There are four major types of compounds, distinguished by how the constituent atoms are bonded together. Molecular compounds are held together by covalent bonds; ionic compounds are held together by ionic bonds; intermetallic compounds are held together by metallic bonds; coordination complexes are held together by coordinate covalent bonds. Non-stoichiometric compounds form a disputed marginal case. A chemical formula specifies the number of atoms of each element in a compound molecule, using the s ...
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Catalysis
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some s ...
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Rate Law
In chemistry, the rate law or rate equation for a reaction is an equation that links the initial or forward reaction rate with the concentrations or pressures of the reactants and constant parameters (normally rate coefficients and partial reaction orders). For many reactions, the initial rate is given by a power law such as :v_0\; =\; k mathrmx mathrmy where and express the concentration of the species and usually in moles per liter (molarity, ). The exponents and are the partial ''orders of reaction'' for and and the ''overall'' reaction order is the sum of the exponents. These are often positive integers, but they may also be zero, fractional, or negative. The constant is the reaction rate constant or ''rate coefficient'' of the reaction. Its value may depend on conditions such as temperature, ionic strength, surface area of an adsorbent, or light irradiation. If the reaction goes to completion, the rate equation for the reaction rate v\; =\; k cex cey applies throughou ...
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Concentration
In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', ''molar concentration'', ''number concentration'', and ''volume concentration''. The concentration can refer to any kind of chemical mixture, but most frequently refers to solutes and solvents in solutions. The molar (amount) concentration has variants, such as normal concentration and osmotic concentration. Etymology The term concentration comes from the word concentrate, from the French , from con– + center, meaning “to put at the center”. Qualitative description Often in informal, non-technical language, concentration is described in a qualitative way, through the use of adjectives such as "dilute" for solutions of relatively low concentration and "concentrated" for solutions of relatively high concentration. To concentrate a solution, one must add more solute (for example, ...
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Product (chemistry)
Products are the species formed from chemical reactions. During a chemical reaction, reactants are transformed into products after passing through a high energy transition state. This process results in the consumption of the reactants. It can be a spontaneous reaction or mediated by catalysts which lower the energy of the transition state, and by solvents which provide the chemical environment necessary for the reaction to take place. When represented in chemical equations, products are by convention drawn on the right-hand side, even in the case of reversible reactions. The properties of products such as their energies help determine several characteristics of a chemical reaction, such as whether the reaction is exergonic or endergonic. Additionally, the properties of a product can make it easier to extract and purify following a chemical reaction, especially if the product has a different state of matter than the reactants. Spontaneous reaction : R \rightarrow P *Where R is r ...
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Rate Equation
In chemistry, the rate law or rate equation for a reaction is an equation that links the initial or forward reaction rate with the concentrations or pressures of the reactants and constant parameters (normally rate coefficients and partial reaction orders). For many reactions, the initial rate is given by a power law such as :v_0\; =\; k mathrmx mathrmy where and express the concentration of the species and usually in moles per liter (molarity, ). The exponents and are the partial ''orders of reaction'' for and and the ''overall'' reaction order is the sum of the exponents. These are often positive integers, but they may also be zero, fractional, or negative. The constant is the reaction rate constant or ''rate coefficient'' of the reaction. Its value may depend on conditions such as temperature, ionic strength, surface area of an adsorbent, or light irradiation. If the reaction goes to completion, the rate equation for the reaction rate v\; =\; k cex cey applies throug ...
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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). Th ...
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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 ...
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Apicophilicity
Apicophilicity is the phenomenon in which electronegative substituents of trigonal bipyramidal pentacoordinate compounds prefer to occupy apical (axial) positions (Lap). The term "apicophilicity" was first proposed by Earl L. Muetterties in 1963 for the structural analysis of pentacoordinate phosphorus fluorides by 19F NMR. Since the apical bonding of a pentacoordinate typical (group 1, 2, 13-18) element compound consists of a 3-center-4-electron bond, in which the electron density is localized on two apical substituents, an arrangement in which electronegative substituents occupy apical positions is more stable. The apicophilicity of a substituent is defined as the difference in energy between two isomeric structures in which the substituent occupies an apical position and an equatorial position (Leq). Experimentally, instead of direct measurement of the energy difference, which is usually difficult to measure, the relative energy barriers for pseudorotation In chemistry, a ps ...
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Potassium Tetrachloroplatinate
Potassium tetrachloroplatinate(II) is the chemical compound with the formula K2PtCl4. This reddish orange salt is an important reagent for the preparation of other coordination complexes of platinum. It consists of potassium cations and the square planar dianion PtCl42−. Related salts are also known including Na2PtCl4, which is brown-colored and soluble in alcohols, and quaternary ammonium salts, which are soluble in a broader range of organic solvents. Preparation Potassium tetrachloroplatinate is prepared by reduction of the corresponding hexachloroplatinate salt with sulfur dioxide. K2PtCl4 is one of the salts that is most easily obtained from platinum ores. The complex is appreciably soluble only in water. Treatment with alcohols, especially in the presence of base, causes reduction to platinum metal. Organic tetrachloroplatinate salts, such as PPN.html" ;"title="/nowiki>PPN">/nowiki>PPN/nowiki>2PtCl4 are soluble in chlorocarbons. Reactions The chloride ligands on ...
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