RATE OF REACTIONS.
The reaction rate (rate of reaction) or speed of reaction for a reactant or product in a particular reaction is intuitively defined as how fast or slow a reaction takes place. For example, the oxidative rusting of iron under the atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second (right). Chemical kinetics is the part of physical chemistry that studies reaction rates. The concepts of chemical kinetics are applied in many disciplines, such as chemical engineering, enzymology and environmental engineering. -------------------------------------------------
Formal definition of reaction rate
Consider a typical chemical reaction:
aA + bB → pP + qQ
The lowercase letters (a, b, p, and q) represent stoichiometric coefficients, while the capital letters represent the reactants (A and B) and the products(P and Q). According to IUPAC's Gold Book definition the reaction rate r for a chemical reaction occurring in a closed system under isochoric conditions, without a build-up of reaction intermediates, is defined as:
where [X] denotes the concentration of the substance X. (Note: The rate of a reaction is always positive. A negative sign is present to indicate the reactant concentration is decreasing.) The IUPAC recommends that the unit of time should always be the second. In such a case the rate of reaction differs from the rate of increase of concentration of a product P by a constant factor (the reciprocal of its stoichiometric number) and for a reactant A by minus the reciprocal of the stoichiometric number. Reaction rate usually has the units of mol L−1 s−1. It is important to bear in mind that the previous definition is only valid for a single reaction, in a closed system of constant volume. This most usually implicit assumption must be stated explicitly, otherwise the definition is incorrect: If water is added to a pot containing salty water, the concentration of salt decreases, although there is no chemical reaction. For any system in general the full mass balance must be taken into account: IN - OUT + GENERATION -CONSUMPTION= ACCUMULATION
When applied to the closed system at constant volume considered previously, this equation reduces to: , where the concentration is related to the number of molecules by . Here is the Avogadro constant. For a single reaction in a closed system of varying volume the so called rate of conversion can be used, in order to avoid handling concentrations. It is defined as the derivative of the extent of reaction with respect to time.
Here is the stoichiometric coefficient for substance, equal to a, b, p, and q in the typical reaction above. Also is the volume of reaction and is the concentration of substance. When side products or reaction intermediates are formed, the IUPAC recommends the use of the terms rate of appearance and rate of disappearance for products and reactants, properly. Reaction rates may also be defined on a basis that is not the volume of the reactor. When a catalyst is used the reaction rate may be stated on a catalyst weight (mol g−1 s−1) or surface area (mol m−2 s−1) basis. If the basis is a specific catalyst site that may be rigorously counted by a specified method, the rate is given in units of s−1 and is called a turnover frequency. -------------------------------------------------
Factors influencing rate of reaction
The nature of the reaction: Some reactions are naturally faster than others. The number of reacting species, their physical state (the particles that form solids move much more slowly than those of gases or those in solution), the complexity of the reaction and other factors can greatly influence the rate of a reaction. Concentration: Reaction rate increases with concentration, as described by the rate law and explained by collision theory. As reactant concentration increases, the frequency of collision increases....
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