Steady State Approximation
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Steady State Approximation
In chemistry, a steady state is a situation in which all state variables are constant in spite of ongoing processes that strive to change them. For an entire system to be at steady state, i.e. for all state variables of a system to be constant, there must be a flow through the system (compare mass balance). A simple example of such a system is the case of a bathtub with the tap running but with the drain unplugged: after a certain time, the water flows in and out at the same rate, so the water level (the state variable Volume) stabilizes and the system is in a steady state. The steady state concept is different from chemical equilibrium. Although both may create a situation where a concentration does not change, in a system at chemical equilibrium, the net reaction rate is zero (products transform into reactants at the same rate as reactants transform into products), while no such limitation exists in the steady state concept. Indeed, there does not have to be a reaction at all f ...
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Chemistry
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during a Chemical reaction, reaction with other Chemical substance, substances. Chemistry also addresses the nature of chemical bonds in chemical compounds. In the scope of its subject, chemistry occupies an intermediate position between physics and biology. It is sometimes called the central science because it provides a foundation for understanding both Basic research, basic and Applied science, applied scientific disciplines at a fundamental level. For example, chemistry explains aspects of plant growth (botany), the formation of igneous rocks (geology), how atmospheric ozone is formed and how environmental pollutants are degraded (ecology), the properties ...
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Reaction Mechanism
In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage of an overall chemical reaction. The detailed steps of a reaction are not observable in most cases. The conjectured mechanism is chosen because it is thermodynamically feasible, and has experimental support in isolated intermediates (see next section) or other quantitative and qualitative characteristics of the reaction. It also describes each reactive intermediate, activated complex, and transition state, and which bonds are broken (and in what order), and which bonds are formed (and in what order). A complete mechanism must also explain the reason for the reactants and catalyst used, the stereochemistry observed in reactants and products, all products formed and the amount of each. The electron or arrow pushing method is often used in i ...
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Reaction Progress Kinetic Analysis
In chemistry, reaction progress kinetic analysis (RPKA) is a subset of a broad range of kinetic techniques utilized to determine the rate laws of chemical reactions and to aid in elucidation of reaction mechanisms. While the concepts guiding reaction progress kinetic analysis are not new, the process was formalized by Professor Donna Blackmond (currently at Scripps Research Institute) in the late 1990s and has since seen increasingly widespread use. Unlike more common pseudo-first-order analysis, in which an overwhelming excess of one or more reagents is used relative to a species of interest, RPKA probes reactions at synthetically relevant conditions (i.e. with concentrations and reagent ratios resembling those used in the reaction when not exploring the rate law.) Generally, this analysis involves a system in which the concentrations of ''multiple'' reactants are changing measurably over the course of the reaction. As the mechanism can vary depending on the relative and absolute ...
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Lindemann Mechanism
In chemical kinetics, the Lindemann mechanism (also called the Lindemann–Christiansen mechanism or the Lindemann–Hinshelwood mechanism) is a schematic reaction mechanism for unimolecular reactions. Frederick Lindemann and J.A. Christiansen proposed the concept almost simultaneously in 1921, and Cyril Hinshelwood developed it to take into account the energy distributed among vibrational degrees of freedom for some reaction steps. It breaks down an apparently unimolecular reaction into two elementary steps, with a rate constant for each elementary step. The rate law and rate equation for the entire reaction can be derived from the rate equations and rate constants for the two steps. The Lindemann mechanism is used to model gas phase decomposition or isomerization reactions. Although the net formula for a decomposition or isomerization appears to be unimolecular and suggests first-order kinetics in the reactant, the Lindemann mechanism shows that the unimolecular reaction step i ...
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Induction Period
An induction period in chemical kinetics is an initial slow stage of a chemical reaction; after the induction period, the reaction accelerates. Ignoring induction periods can lead to runaway reactions. In some catalytic reactions, a pre-catalyst needs to undergo a transformation to form the active catalyst, before the catalyst can take effect. Time is required for this transformation, hence the induction period. For example, with Wilkinson's catalyst, one triphenylphosphine ligand must dissociate to give the coordinatively unsaturated 14-electron species which can participate in the catalytic cycle: : Similarly, for an autocatalytic reaction, where one of the reaction products catalyzes the reaction itself, the rate of reaction is low initially until sufficient products have formed to catalyze the reaction. Reactions generally accelerate when heat is applied. Where a reaction is exothermic, the rate of the reaction may initially be low. As the reaction proceeds, heat is generat ...
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Radioactive Decay
Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is considered radioactive. Three of the most common types of decay are alpha decay ( ), beta decay ( ), and gamma decay ( ), all of which involve emitting one or more particles. The weak force is the mechanism that is responsible for beta decay, while the other two are governed by the electromagnetism and nuclear force. A fourth type of common decay is electron capture, in which an unstable nucleus captures an inner electron from one of the electron shells. The loss of that electron from the shell results in a cascade of electrons dropping down to that lower shell resulting in emission of discrete X-rays from the transitions. A common example is iodine-125 commonly used in medical settings. Radioactive decay is a stochastic (i.e. random) proce ...
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Reactions On Surfaces
Reactions on surfaces are reactions in which at least one of the steps of the reaction mechanism is the adsorption of one or more reactants. The mechanisms for these reactions, and the rate equations are of extreme importance for heterogeneous catalysis. Via scanning tunneling microscopy, it is possible to observe reactions at the solid gas interface in real space, if the time scale of the reaction is in the correct range. Reactions at the solid–gas interface are in some cases related to catalysis. Simple decomposition If a reaction occurs through these steps: : A + S ⇌ AS → Products where A is the reactant and S is an adsorption site on the surface and the respective rate constants for the adsorption, desorption and reaction are ''k''1, ''k''−1 and ''k''2, then the global reaction rate is: :r=k_2 C_\mathrm=k_2 \theta C_\mathrm where: * ''r'' is the rate, mol·''m''−2·s−1 *C_Ais the concentration of adsorbate, ''mol·m−3'' *C_\mathrm is the surface concentrati ...
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Heterogeneous
Homogeneity and heterogeneity are concepts often used in the sciences and statistics relating to the uniformity of a substance or organism. A material or image that is homogeneous is uniform in composition or character (i.e. color, shape, size, weight, height, distribution, texture, language, income, disease, temperature, radioactivity, architectural design, etc.); one that is heterogeneous is distinctly nonuniform in at least one of these qualities. Heterogeneous Mixtures, in chemistry, is where certain elements are unwillingly combined and, when given the option, will separate. Etymology and spelling The words ''homogeneous'' and ''heterogeneous'' come from Medieval Latin ''homogeneus'' and ''heterogeneus'', from Ancient Greek ὁμογενής (''homogenēs'') and ἑτερογενής (''heterogenēs''), from ὁμός (''homos'', “same”) and ἕτερος (''heteros'', “other, another, different”) respectively, followed by γένος (''genos'', “kind”); - ...
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Closed-form Expression
In mathematics, a closed-form expression is a mathematical expression that uses a finite number of standard operations. It may contain constants, variables, certain well-known operations (e.g., + − × ÷), and functions (e.g., ''n''th root, exponent, logarithm, trigonometric functions, and inverse hyperbolic functions), but usually no limit, differentiation, or integration. The set of operations and functions may vary with author and context. Example: roots of polynomials The solutions of any quadratic equation with complex coefficients can be expressed in closed form in terms of addition, subtraction, multiplication, division, and square root extraction, each of which is an elementary function. For example, the quadratic equation :ax^2+bx+c=0, is tractable since its solutions can be expressed as a closed-form expression, i.e. in terms of elementary functions: :x=\frac. Similarly, solutions of cubic and quartic (third and fourth degree) equations can be expresse ...
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