Cairo University, Faculty of Science, Chemistry Department

Chemical kinetics or reaction kinetics is the study of reaction rates in a chemical reaction. Analyzing the influence of different reaction conditions on the reaction rate gives information about the reaction mechanism and the transition state of a chemical reaction. In 1864, Peter Waage 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. Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with a physical change of state within the confines of the laws of thermodynamics. The power of thermodynamics lies in the fact that useful information is obtained by considering only the initial and the final states of a system; intermediate states are not described. The description of the mode or mechanism of a chemical reaction is beyond the scope of the thermodynamics. This is the difference between thermodynamics and kinetics. Thermodynamics can tell you only that a reaction should go because the products are more stable (have a lower free energy) than the reactants. Another way of saying this is that the free energy change (the second law of thermodynamics) of the reaction is negative and therefore the reaction is spontaneous. Yet another way of saying this is to say that the reaction has a large equilibrium constant, signifying that if nature could ever attain equilibrium, there would be many more products present than there are reactants. Notice that the G = RT lnK equation says all this at once. Kinetics, on the other hand, can tell you how fast the reaction will go but doesn't tell you anything about the final state of things once it gets there. Kinetics does not depend on what the situation looks like at equilibrium. The rate of the reaction has no dependence on the overall reaction equation but instead depends on the reaction mechanism, the elementary steps. It might be assumed that the more the free energy is lowered in a reaction, the faster the reaction will proceed. This assumption is not correct; predictions based on thermodynamics take into consideration only the initial and the final states of the system. Nothing is assumed about the rate or path or mechanism for going from one state to another. Applied to chemistry, the useful result of obtaining values for free energy changes for various reactions is the ability to determine whether a given reaction can occur spontaneously. For example, a calculation shows that the reaction H2(g) + 1/2O2(g) H2O(l) G is 56.7 kcal/mole at 298 K. The negative value of G indicates that the reaction should proceed spontaneously; yet a mixture of hydrogen gas and oxygen gas will remain indefinitely at room temperature without reacting. However, in the presence of a catalyst, such as finely divided platinum, such a mixture would be converted rapidly and smoothly at room temperature into water. According to the collision theory, the reaction energy diagram 1

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has the shape shown in figure 1 where the reactants cross over a transition state before they reduce finally to the products (c.f. the attached picture). As can be seen from the figure the transition state lies at higher energy and this is because it is highly unstable. Therefore, the reactants should have the enough energy in order to surmount this energy barrier which is now known as activation energy. Activation energy is thereby seen as the energetic barrier that prevents the second law from being obeyed instantly.

Fig (1) The above example points out the difference between the concepts of kinetic stability and thermodynamic stability, many systems are thermodynamically unstable at ordinary temperatures and exist only because the rate at which they react is low. Such systems are stable in a kinetic sense only, and if some change which increases the rate of the reaction is made, the predicted reaction will occur spontaneously. So, the importance of chemical kinetics lies in the following points: Kinetic measurements provide insight into the mechanism of complex reactions. Kinetics can explain: Why some reactions are fast and some are slow? Why do the rates of some reactions show temperature dependence? How to promote a particular reaction? Molecularity and order: Some reactions occur in one step, while others require multiple steps. Molecularity refers to the number of molecules consumed in a reaction. When a single molecule is consumed, the step is called unimolecular. When two molecules are consumed, the step is called bimolecular. The molecularity of a reaction describes what happens on the molecular level The order of a reaction describes what happens on the macroscopic scale. It is determined experimentally. It is only for elementary steps that the rate is proportional to the product of the reactant concentrations, i.e. reaction order = molecularity. Rate of reaction: Kinetics deal with the experimental determination of reaction rates from which a rate law and reaction rate constant are derived: General reaction: aA + bB cC + dD General rate law: Rate = k[A]x[B]y

Cairo University, Faculty of Science, Chemistry Department

Note that there exists no relationship between the powers x and y and the stoichiometry of the reaction. Sometimes the rate law follows the stoichiometry of the reaction, but this is usually coincidental! Overall reaction order: sum of powers to which all reactant concentrations in rate law raised (= x + y). It is an indication of how the reaction takes place (with respect to each reactant). In summary, the rate laws for chemical reactions can be explained by the following rules: The rate of any step in a reaction is directly proportional to the concentrations of the reagents consumed in that step. The overall rate law for a reaction is determined by the sequence of steps, or the mechanism, by which reactants are converted into products.

Factors influencing rate of reaction

There are several factors that affect the rate of 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 and so does the fraction of collisions having sufficient energy to cause 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 influence greatly the rate of a reaction. Temperature: Conducting a reaction at a higher temperature delivers more energy into the system and increases the reaction rate by causing more collisions between particles, as explained by collision theory. However, the main reason why it increases the rate of reaction is that more of the colliding particles will have the necessary activation energy resulting in more successful collisions. As a rough rule of thumb, reaction rates for many reactions double or triple for every 10 degrees Celsius increase in temperature. The influence of temperature is described by the Arrhenius equation;

k = Ae-Ea/RT
where k is the rate constant for the reaction, A is a constant called the preexponential factor or the frequency factor,its related to the probability of successful collision, Ea is the energy of activation,it represents the height of the hump on the reaction diagram fig (1), R is the general gas constant, and T is the absolute temperature. Taking the natural logarithm for the Arrhenius equation, ln k = ln A - Ea/RT Therefore, a plot of ln k versus 1/T gives a straight line with intercept ln A (from which A can be determined), and slope -Ea/R from which the activation energy of the reaction can be determined. See fig (2).

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Fig 2

Solvent: Many reactions take place in solution and the properties of the solvent affect the reaction rate. The ionic strength as well has an effect on reaction rate. Pressure: The rate of gaseous reactions increases with pressure, which is, in fact, equivalent to an increase in concentration of the gas. Electromagnetic Radiation: Electromagnetic radiation is a form of energy so it may speed up the rate or even make a reaction spontaneous, as it provides the particles of the reactants with more energy. For example, when methane reacts with chlorine in the dark, the reaction rate is very slow. It can be speeded up when the mixture is put under diffused light. In bright sunlight, the reaction is explosive. A catalyst: The presence of a catalyst increases the reaction rate by providing an alternative pathway with lower activation energy (see fig (3)). The effect of this is that more molecular collisions have the energy needed to reach the transition state. Hence, catalysts can perform reactions that, albeit thermodynamically feasible, would not run without the presence of a catalyst, or perform them much faster, more specific, or at lower temperatures.For example, platinum catalyzes the combustion of hydrogen with oxygen at room temperature. Fig. 3

Isotopes: The kinetic isotope effect consists in a different reaction rate for the same molecule if it has different isotopes, usually hydrogen isotopes, because of the mass difference between protium and deuterium. Surface Area: In reactions on surfaces, which take place for example during heterogeneous catalysis (where the reaction is limited to the interface between the reactants, i.e. at the area of contact), the rate of reaction increases as the surface area does. That is due to the fact that more particles of the solid are exposed and can be hit by reactant molecules (see fig. 4) 4

Cairo University, Faculty of Science, Chemistry Department Fig. 4

Order: The order of the reaction controls how the reactant concentration affects reaction rate.

All the factors that affect a reaction rate are taken into account in the rate equation of the reaction.

Cairo University, Faculty of Science, Chemistry Department

Table, summary of the rate equations characteristic for each reaction order Rex. order Differential form of rate eqn. Integral form of rate eqn. Dimension of k t1/2 half life time

plot

Slope

zero

dx/dt = k

k = x/t

(mol/l).t-1

t1/2 = a/2k

first

dx/dt = k(a-x)

k = 2.303/t [log(a/a-x)]

t-1

t1/2 = 0.693/k

-k/2.303

second a=b

dx/dt = k (a-x)2

k = x/[at(a-x)]

(mol/l)-1t-1

t1/2 = 1/ka

third a=b=c

dx/dt = k (a-x)3

k=1/2t{x(2a-x)/ a2(a-x)2}

(mol/l)-2t-1

t1/2 = 3/2ka2

2k

Cairo University, Faculty of Science, Chemistry Department

Two essential problems concerning chemical reactions made the scientists worried about for a long period:
1. How can we predict whether or not a reaction will take place? The answer to this question comes from thermodynamics

Thermodynamics,
predicts

Reaction direction
G = ve Spontaneous in this direction G = zero Reaction at equilibrium G = + ve
Spontaneous in the opposite direction

Reaction extent
When does the reaction comes to an end? Keq

G = RT ln Keq

2. Once started, how fast does the reaction proceed? Chemical kinetics has the answer to this question, "The area of chemistry concerned with the speeds, or rates, at which a chemical reaction occurs" Kinetics usually plays an important role in industrial processes, since the products must be manufactured in the minimum time under the most economical conditions. Consider the synthesis of polyethylene, toys, and mailer envelopes. Polyethylene is a polymer, which is a molecule of very high molar mass (thousands to hundreds of thousands of grams). It is made by joining many units of ethylene molecules (called monomers) together in a process called polymerization. Studying the kinetics of formation of polyethylene is a necessary prerequisite for the attempt of producing such a polymer at lower time and using lower energy. This is to be accomplished using the appropriate catalyst. Catalyst efficiency is usually justified on how much it decreased the energy of activation of polymer formation and on to how much the time of polymer formation is reduced. Another important example is Ammonia which is an extremely valuable inorganic substance used in the fertilizer industry, the manufacture of explosives, and many other applications. Around the turn of the century, many chemists strove to synthesize ammonia from nitrogen and hydrogen. The supply of atmospheric nitrogen is virtually inexhaustible, and hydrogen gas can be produced readily by passing steam over heated coal: 7

Cairo University, Faculty of Science, Chemistry Department

H2O(g) + C(s)

CO(g) + H2(g)

Hydrogen is also obtained as a by-product of petroleum refining. The formation of NH3 from N2 and H2 is exothermic: N2(g) + 3H2(g) 2NH3(g) Ho = 92.6 kJ

But the reaction rate is extremely slow at room temperature. To be practical on a large scale, a reaction must occur at an appreciable rate and it must have a high yield of the desired product. Raising the temperature does accelerate the above reaction, but at the same time it promotes the decomposition of NH3 molecules into N2 and H2 thus lowering the yield of NH3. In 1905, after testing literally hundreds of compounds at various temperatures and pressures, Fritz Haber discovered that iron plus a few percent of oxides of potassium and aluminum catalyze the reaction of hydrogen with nitrogen to yield ammonia at about 500oC. This procedure is known as the Haber process. In heterogeneous catalysis, the surface of the solid catalyst is usually the site of the reaction. The initial step in the Haber process involves the dissociation of N2 and H2 on the metal surface (c.f. Figure 5). Although the dissociated species are not truly free atoms because they are bonded to the metal surface, they are highly reactive. The two dissociates into atomic hydrogen at temperatures as low as 196oC (the boiling point of liquid nitrogen). Nitrogen molecules, on the other hand, dissociates at about 500oC. The highly reactive N and H atoms combine rapidly at high temperatures to produce the desired NH3 molecules: N + 3H NH3

H2 N2 NH3

Fig (5)