Which rate law is termolecular

Chemical reactions very often occur in a step-wise fashion, involving two or more distinct reactions taking place in sequence. A balanced equation indicates what is reacting and what is produced, but it reveals no details about how the reaction actually takes place. The reaction mechanism or reaction path provides details regarding the precise, step-by-step process by which a reaction occurs. The decomposition of ozone, for example, appears to follow a mechanism with two steps:.

Each of the steps in a reaction mechanism is an elementary reaction. These elementary reactions occur precisely as represented in the step equations, and they must sum to yield the balanced chemical equation representing the overall reaction:.

Notice that the oxygen atom produced in the first step of this mechanism is consumed in the second step and therefore does not appear as a product in the overall reaction. Species that are produced in one step and consumed in a subsequent step are called intermediates.

While the overall reaction equation for the decomposition of ozone indicates that two molecules of ozone react to give three molecules of oxygen, the mechanism of the reaction does not involve the direct collision and reaction of two ozone molecules. Instead, one O 3 decomposes to yield O 2 and an oxygen atom, and a second O 3 molecule subsequently reacts with the oxygen atom to yield two additional O 2 molecules.

Unlike balanced equations representing an overall reaction, the equations for elementary reactions are explicit representations of the chemical change taking place. For this reason, the rate law for an elementary reaction may be derived directly from the balanced chemical equation describing the reaction. This is not the case for typical chemical reactions, for which rate laws may be reliably determined only via experimentation.

The molecularity of an elementary reaction is the number of reactant species atoms, molecules, or ions. For example, a unimolecular reaction involves the reaction of a single reactant species to produce one or more molecules of product:. A unimolecular reaction may be one of several elementary reactions in a complex mechanism.

For example, the reaction:. However, some unimolecular reactions may be the only step of a single-step reaction mechanism.

For example, the gas-phase decomposition of cyclobutane, C 4 H 8 , to ethylene, C 2 H 4 , is represented by the following chemical equation:. This equation represents the overall reaction observed, and it might also represent a legitimate unimolecular elementary reaction. The rate law predicted from this equation, assuming it is an elementary reaction, turns out to be the same as the rate law derived experimentally for the overall reaction, namely, one showing first-order behavior:.

This agreement between observed and predicted rate laws is interpreted to mean that the proposed unimolecular, single-step process is a reasonable mechanism for the butadiene reaction. A bimolecular reaction involves two reactant species, for example:. For the first type, in which the two reactant molecules are different, the rate law is first-order in A and first order in B second-order overall :.

For the second type, in which two identical molecules collide and react, the rate law is second order in A :. Some chemical reactions occur by mechanisms that consist of a single bimolecular elementary reaction. One example is the reaction of nitrogen dioxide with carbon monoxide:. Bimolecular elementary reactions may also be involved as steps in a multistep reaction mechanism. The reaction of atomic oxygen with ozone is the second step of the two-step ozone decomposition mechanism discussed earlier in this section:.

An elementary termolecular reaction involves the simultaneous collision of three atoms, molecules, or ions. Termolecular elementary reactions are uncommon because the probability of three particles colliding simultaneously is less than one one-thousandth of the probability of two particles colliding. There are, however, a few established termolecular elementary reactions.

The reaction of nitric oxide with oxygen appears to involve termolecular steps:. Likewise, the reaction of nitric oxide with chlorine appears to involve termolecular steps:. Because a reaction cannot proceed faster than its slowest step, this step will limit the rate at which the overall reaction occurs. The slowest step is therefore called the rate-limiting step or rate-determining step of the reaction Figure.

As described earlier, rate laws may be derived directly from the chemical equations for elementary reactions. This is not the case, however, for ordinary chemical reactions. The balanced equations most often encountered represent the overall change for some chemical system, and very often this is the result of some multistep reaction mechanisms. In every case, the rate law must be determined from experimental data and the reaction mechanism subsequently deduced from the rate law and sometimes from other data.

The reaction of NO 2 and CO provides an illustrative example:. The reaction is first order with respect to NO 2 and first-order with respect to CO. This is consistent with a single-step bimolecular mechanism and it is possible that this is the mechanism for this reaction at high temperatures.

This rate law is not consistent with the single-step mechanism, but is consistent with the following two-step mechanism:. The rate-determining slower step gives a rate law showing second-order dependence on the NO 2 concentration, and the sum of the two equations gives the net overall reaction.

In general, when the rate-determining slower step is the first step in a mechanism, the rate law for the overall reaction is the same as the rate law for this step. However, when the rate-determining step is preceded by a step involving a rapidly reversible reaction the rate law for the overall reaction may be more difficult to derive.

As discussed in several chapters of this text, a reversible reaction is at equilibrium when the rates of the forward and reverse processes are equal. Consider the reversible elementary reaction in which NO dimerizes to yield an intermediate species N 2 O 2. When this reaction is at equilibrium:. Cell Biology Video Lessons. Genetics Video Lessons. Biochemistry Video Lessons. GOB Video Lessons. Microbiology Video Lessons. Calculus Video Lessons. Statistics Video Lessons.

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Problem : Which rate law is termolecular? See all problems in Reaction Mechanism. Frequently Asked Questions What scientific concept do you need to know in order to solve this problem?