activation energy
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activation energy
(′ak·tə′vā·shən ′en·ər·jē)
(physical chemistry) The energy, in excess over the ground state, which must be added to an atomic or molecular system to allow a particular process to take place.
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activation energy
Minimum amount of energy (heat, electromagnetic radiation, or electrical energy) required to activate atoms or molecules to a condition in which it is equally likely that they will undergo chemical reaction or transport as it is that they will return to their original state. Chemists posit a transition state between the initial conditions and the product conditions and theorize that the activation energy is the amount of energy required to boost the initial materials uphill to the transition state; the reaction then proceeds downhill to form the product materials. Catalysts (including enzymes) lower the activation energy by altering the transition state. Activation energies are determined by experiments that measure them as the constant of proportionality in the equation describing the dependence of reaction rate on temperature, proposed by Svante Arrhenius. entropy, heat of reaction.
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activation energy
activation energy, in chemistry, minimum energy needed to cause a chemical reaction. A chemical reaction between two substances occurs only when an atom, ion, or molecule of one collides with an atom, ion, or molecule of the other. Only a fraction of the total collisions result in a reaction, because usually only a small percentage of the substances interacting have the minimum amount of kinetic energy a molecule must possess for it to react. When the reactants collide, they may form an intermediate product whose chemical energy is higher than the combined chemical energy of the reactants. In order for this transition state in the reaction to be achieved, some energy must enter into the reaction other than the chemical energy of the reactants. This energy is the activation energy. Once the intermediate product, or activated complex, is formed, the final products are formed from it. The path from reactants through the activated complex to the final products is known as the reaction mechanism. (Reaction mechanisms for complex reactions may involve several steps analogous to that described here.) Because the heat energy of a substance is not uniformly distributed among its atoms, ions, or molecules, some may carry enough heat energy to react while others do not. If the activation energy is low, a greater proportion of the collisions between reactants will result in reactions. If the temperature of the system is increased, the average heat energy is increased, a greater proportion of collisions between reactants result in reaction, and the reaction proceeds more rapidly. A catalyst increases the reaction rate by providing a reaction mechanism with a lower activation energy, so that a greater proportion of collisions result in reaction. The activation energy and rate of a reaction are related by the equation k=Aexp(−Ea/RT), where k is the rate constant, A is a temperature-independent constant (often called the frequency factor), exp is the function ex, Ea is the activation energy, R is the universal gas constant, and T is the temperature. This relationship was derived by Arrhenius in 1899. Because the relationship of reaction rate to activation energy and temperature is exponential, a small change in temperature or activation energy causes a large change in the rate of the reaction. Activation energies are usually determined experimentally by measuring the reaction rate k at different temperatures T, plotting the logarithm of k against 1/T on a graph, and determining the slope of the straight line that best fits the points.
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categories related to 'activation energy'
- Chemical Properties and Reactions - activation energy: energy required to start a chemical reaction
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Activation energy
In chemistry, activation energy is a term introduced in 1889 by the Swedish scientist Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occur. Activation energy may also be defined as the minimum energy required to start a chemical reaction. The activation energy of a reaction is usually denoted by Ea, and given in units of kilojoules per mole.
Activation energy can be thought of as the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and products of a reaction). For a chemical reaction to proceed at a reasonable rate, there should exist an appreciable number of molecules with energy equal to or greater than the activation energy.
At a more advanced level, the Arrhenius Activation energy term from the Arrhenius equation is best regarded as an experimentally determined parameter that indicates the sensitivity of the reaction rate to temperature. There are two objections to associating this activation energy with the threshold barrier for an elementary reaction. First, it is often unclear as to whether or not reaction does proceed in one step; threshold barriers that are averaged out over all elementary steps have little theoretical value. Second, even if the reaction being studied is elementary, a spectrum of individual collisions contributes to rate constants obtained from bulk ('bulb') experiments involving billions of molecules, with many different reactant collision geometries and angles, different translational and (possibly) vibrational energies - all of which may lead to different microscopic reaction rates.
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Negative activation energy
In some cases, rates of reaction decrease with increasing temperature. When following an approximately exponential relationship so the rate constant can still be fit to an Arrhenius expression, this results in a negative value of Ea. Elementary reactions exhibiting these negative activation energies are typically barrierless reactions, in which the reaction proceeding relies on the capture of the molecules in a potential well. Increasing the temperature leads to a reduced probability of the colliding molecules capturing one another (with more glancing collisions not leading to reaction as the higher momentum carries the colliding particles out of the potential well), expressed as a reaction cross section that decreases with increasing temperature. Such a situation no longer leads itself to direct interpretations as the height of a potential spot.
Temperature independence and the relation to the Arrhenius equation
The Arrhenius equation gives the quantitative basis of the relationship between the activation energy and the rate at which a reaction proceeds. From the Arrhenius equation, the activation energy can be expressed as
where A is the frequency factor for the reaction, R is the universal gas constant, T is the temperature (in kelvins), and k is the reaction rate coefficient. While this equation suggests that the activation energy is dependent on temperature, in regimes in which the Arrhenius equation is valid this is cancelled by the temperature dependence of k. Thus, Ea can be evaluated from the reaction rate coefficient at any temperature (within the validity of the Arrhenius equation).
Catalysis
Main article: Catalysis
) and enthalpy of formation (ΔH) with and without a catalyst, plotted against the reaction coordinate. The highest energy position (peak position) represents the transition state. With the catalyst, the energy required to enter transition state decreases, thereby decreasing the energy required to initiate the reaction.A substance that modifies the transition state to lower the activation energy is termed a catalyst; a biological catalyst is termed an enzyme. It is important to note that a catalyst increases the rate of reaction without being consumed by it. In addition, while the catalyst lowers the activation energy, it does not change the energies of the original reactants or products. Rather, the reactant energy and the product energy remain the same and only the activation energy is altered (lowered).
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