Chemical kinetics, also known as reaction kinetics, is the study of
rates of chemical processes. Chemical kinetics includes investigations of how different experimental conditions can 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 can describe the characteristics of a chemical reaction. 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.
Rate of reaction
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Main article: reaction rate
Chemical kinetics deals with the experimental determination of reaction rates from which rate laws and rate constants are derived. Relatively simple rate laws exist for zero order reactions (for which reaction rates are independent of concentration), first order reactions, and second order reactions, and can be derived for others. In consecutive reactions the rate-determining step often determines the kinetics. In consecutive first order reactions, a steady state approximation can simplify the rate law. The activation energy for a reaction is experimentally determined through the Arrhenius equation and the Eyring equation. The main factors that influence the reaction rate include: the physical state of the reactants, the concentrations of the reactants, the temperature at which the reaction occurs, and whether or not any catalysts are present in the reaction.
Factors affecting reaction rate
Nature of the Reactants
Depending upon what substances are reacting, the time varies. Acid reactions, the formation of salts, and ion exchange are fast reactions. When covalent bond formation takes place between the molecules and when large molecules are formed, the reactions tend to be very slow.
Physical State
The physical state (solid, liquid, or gas) of a reactant is also an important factor of the rate of change. When reactants are in the same phase, as in aqueous solution, thermal motion brings them into contact. However, when they are in different phases, the reaction is limited to the interface between the reactants. Reaction can only occur at their area of contact, in the case of a liquid and a gas, at the surface of the liquid. Vigorous shaking and stirring may be needed to bring the reaction to completion. This means that the more finely divided a solid or liquid reactant, the greater its surface area per unit volume, and the more contact it makes with the other reactant, thus the faster the reaction. To make an analogy, for example, when one starts a fire, one uses wood chips and small branches—one doesn't start with large logs right away. In organic chemistry On water reactions are the exception to the rule that homogeneous reactions take place faster than heterogeneous reactions.
Concentration
Concentration plays an important role in reactions according to the collision theory of chemical reactions, this is because molecules must collide in order to react together. As the concentration of the reactants increases, the frequency of the molecules colliding increases, striking each other faster by being in closer contact at any given point in time. Imagine two reactants being in a closed container. All the molecules contained within are colliding constantly. By increasing the amount of one or more of the reactants you cause these collisions to happen more often, increasing the reaction rate (Figure 1.1).
Temperature
Temperature usually has a major effect on the rate of a chemical reaction. Molecules at a higher temperature have more thermal energy. Although collision frequency is greater at higher temperatures, this alone contributes only a very samll proportion to the increase in rate of reaction. Much more important is the fact that the proportion of reactant molecules with sufficient energy to react (energy greater than activation energy: E > Ea) is significantly higher and is explained in detail by the Maxwell-Boltzmann distribution of molecular energies.
The 'rule of thumb' that the rate of chemical reactions double for every 10 °C temperature rise is a common misconception. This may have been generalized from the special case of biological systems, where the Q10 (temperature coefficient) is often between 1.5 and 2.5.
A reaction's kinetics can also be studied with a temperature jump approach. This involves using a sharp rise in temperature and observing the relaxation rate of an equilibrium process.
Catalysts
Generic potential energy diagram showing the effect of a catalyst in an hypothetical exothermic chemical reaction. The presence of the catalyst opens a different reaction pathway (shown in red) with a lower activation energy. The final result and the overall thermodynamics are the same.
A catalyst is a substance that accelerates the rate of a chemical reaction but remains chemically unchanged afterwards. The catalyst increases rate reaction by providing a different reaction mechanism to occur with a lower activation energy. In autocatalysis a reaction product is itself a catalyst for that reaction leading to positive feedback. Proteins that act as catalysts in biochemical reactions are called enzymes. Michaelis-Menten kinetics describe the rate of enzyme mediated reactions.
In certain organic molecules specific substituents can have an influence on reaction rate in neighbouring group participation.
Agitating or mixing a solution will also accelerate the rate of a chemical reaction, as this gives the particles greater kinetic energy, increasing the number of collisions between reactants and therefore the possibility of successful collisions.
Increasing the pressure in a gaseous reaction will increase the number of collisions between reactants, increasing the rate of reaction. This is because the activity of a gas is directly proportional to the partial pressure of the gas. This is similar to the effect of increasing the concentration of a solution. A catalyst does not affect the position of the equilibria, as the catalyst speeds up the backward and forward reactions equally.
Equilibrium
While chemical kinetics is concerned with the rate of a chemical reaction, thermodynamics determines the extent to which reactions occur. In a reversible reaction, chemical equilibrium is reached when the rates of the forward and reverse reactions are equal and the concentrations of the reactants and products no longer change. This is demonstrated by, for example, the Haber-Bosch process for combining nitrogen and hydrogen to produce ammonia. Chemical clock reactions such as the Belousov-Zhabotinsky reaction demonstrate that component concentrations can oscillate for a long time before finally reaching equilibrium.
Free energy
In general terms, the free energy change (ΔG) of a reaction determines if a chemical change will take place, but kinetics describes how fast the reaction is. A reaction can be very exothermic and have a very positive entropy change but will not happen in practice if the reaction is too slow. If a reactant can produce two different products, the thermodynamically most stable one will generally form except in special circumstances when the reaction is said to be under kinetic reaction control. The Curtin-Hammett principle applies when determining the product ratio for two reactants interconverting rapidly, each going to a different product. It is possible to make predictions about reaction rate constants for a reaction from Free-energy relationships.
The kinetic isotope effect is the difference in the rate of a chemical reaction when an atom in one of the reactants is replaced by one of its isotopes.
Chemical kinetics provides information on residence time and heat transfer in a chemical reactor in chemical engineering and the molar mass distribution in polymer chemistry.
Applications
The mathematical models that describe chemical reaction kinetics provide chemists and chemical engineers with tools to better understand and describe chemical processes such as food decomposition, microorganism growth, stratospheric ozone decomposition, and the complex chemistry of biological systems. These models can also be used in the design or modification of chemical reactors to optimize product yield, more efficiently separate products, and eliminate environmentally harmful by-products. When performing catalytic cracking of heavy hydrocarbons into gasoline and light gas, for example, kinetic models can be used to find the temperature and pressure at which the highest yield of heavy hydrocarbons into gasoline will occur.
