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14.1 Factors That Affect Reaction Rates

Learning Objective

To understand the factors that affect reaction rates.

Although a balanced chemical equation for a reaction describes the quantitative relationships between the amounts of reactants present and the amounts of products that can be formed, it gives us no information about whether or how fast a given reaction will occur. This information is obtained by studying the chemical kinetics of a reaction, which depend on various factors: reactant concentrations, temperature, physical states and surface areas of reactants, and solvent and catalyst properties if either are present. By studying the kinetics of a reaction, chemists gain insights into how to control reaction conditions to achieve a desired outcome.

Concentration Effects

Two substances cannot possibly react with each other unless their constituent particles (molecules, atoms, or ions) come into contact. If there is no contact, the reaction rate will be zero. Conversely, the more reactant particles that collide per unit time, the more often a reaction between them can occur. Consequently, the reaction rate usually increases as the concentration of the reactants increases. One example of this effect is the reaction of sucrose (table sugar) with sulfuric acid, which is shown in Figure 14.1 "The Effect of Concentration on Reaction Rates".

Temperature Effects

You learned in Chapter 10 "Gases" that increasing the temperature of a system increases the average kinetic energy of its constituent particles. As the average kinetic energy increases, the particles move faster, so they collide more frequently per unit time and possess greater energy when they collide. Both of these factors increase the reaction rate. Hence the reaction rate of virtually all reactions increases with increasing temperature. Conversely, the reaction rate of virtually all reactions decreases with decreasing temperature. For example, refrigeration retards the rate of growth of bacteria in foods by decreasing the reaction rates of biochemical reactions that enable bacteria to reproduce. Figure 14.2 "The Effect of Temperature on Reaction Rates" shows how temperature affects the light emitted by two chemiluminescent light sticks.

In systems where more than one reaction is possible, the same reactants can produce different products under different reaction conditions. For example, in the presence of dilute sulfuric acid and at temperatures around 100°C, ethanol is converted to diethyl ether:

Equation 14.1

At 180°C, however, a completely different reaction occurs, which produces ethylene as the major product:

Equation 14.2

Phase and Surface Area Effects

When two reactants are in the same fluid phase, their particles collide more frequently than when one or both reactants are solids (or when they are in different fluids that do not mix). If the reactants are uniformly dispersed in a single homogeneous solution, then the number of collisions per unit time depends on concentration and temperature, as we have just seen. If the reaction is heterogeneous, however, the reactants are in two different phases, and collisions between the reactants can occur only at interfaces between phases. The number of collisions between reactants per unit time is substantially reduced relative to the homogeneous case, and, hence, so is the reaction rate. The reaction rate of a heterogeneous reaction depends on the surface area of the more condensed phase.

Automobile engines use surface area effects to increase reaction rates. Gasoline is injected into each cylinder, where it combusts on ignition by a spark from the spark plug. The gasoline is injected in the form of microscopic droplets because in that form it has a much larger surface area and can burn much more rapidly than if it were fed into the cylinder as a stream. Similarly, a pile of finely divided flour burns slowly (or not at all), but spraying finely divided flour into a flame produces a vigorous reaction ( Figure 14.3 "The Effect of Surface Area on Reaction Rates"). Similar phenomena are partially responsible for dust explosions that occasionally destroy grain elevators or coal mines.

Solvent Effects

The nature of the solvent can also affect the reaction rates of solute particles. For example, a sodium acetate solution reacts with methyl iodide in an exchange reaction to give methyl acetate and sodium iodide.

Equation 14.3

This reaction occurs 10 million times more rapidly in the organic solvent dimethylformamide [DMF; (CH ₃) ₂NCHO] than it does in methanol (CH ₃ OH). Although both are organic solvents with similar dielectric constants (36.7 for DMF versus 32.6 for methanol), methanol is able to hydrogen bond with acetate ions, whereas DMF cannot. Hydrogen bonding reduces the reactivity of the oxygen atoms in the acetate ion.

Solvent viscosity is also important in determining reaction rates. In highly viscous solvents, dissolved particles diffuse much more slowly than in less viscous solvents and can collide less frequently per unit time. Thus the reaction rates of most reactions decrease rapidly with increasing solvent viscosity.

Catalyst Effects

You learned in Chapter 3 "Chemical Reactions" that a catalyst is a substance that participates in a chemical reaction and increases the reaction rate without undergoing a net chemical change itself. Consider, for example, the decomposition of hydrogen peroxide in the presence and absence of different catalysts ( Figure 14.4 "The Effect of Catalysts on Reaction Rates"). Because most catalysts are highly selective, they often determine the product of a reaction by accelerating only one of several possible reactions that could occur.

Most of the bulk chemicals produced in industry are formed with catalyzed reactions. Recent estimates indicate that about 30% of the gross national product of the United States and other industrialized nations relies either directly or indirectly on the use of catalysts.

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To understand the factors that affect reaction rates. Although a balanced chemical equation for a reaction describes the quantitative relationships between the amounts of reactants present and the amounts of products that can be formed, it gives us no information about whether or how fast a given reaction will occur.