
(a)
Interpretation:
Among the given experiments the one that has valid mechanism has to be predicted.
Concept introduction:
Rate law or rate equation: The relationship between the reactant concentrations and reaction rate is expressed by an equation.
Order of a reaction: The order of a reaction with respect to a particular reactant is the exponent of its concentration term in the rate law expression, and the overall reaction order is the sum of the exponents on all concentration terms.
Rate constant, k: It is a proportionality constant that relates rate and concentration at a given temperature.
(a)

Explanation of Solution
- Experiment (1):
The given reaction is one-step collision, hence the reaction equation becomes,
The given actual rate law, is
Therefore, the rate law of the slow step is,
- Experiment (2):
The given reaction involves multiple mechanism steps, by adding the entire individual steps gives rise to an overall reaction equation. Hence, the reaction equation as follows,
The overall equation becomes,
In the reaction, the slow step is the rate determining step; and its rate law is the overall rate law.
Therefore, the rate law of the slow step is,
The concentration
The rate law for the given mechanism steps are,
The rate of mechanism (1),
Thus, by substituting above relation into the equation (1), the rate law becomes,
Therefore, the given rate law is consistent with the rate law of overall reaction obtained as above.
- Experiment (3):
The given reaction involves multiple mechanism steps, by adding the entire individual steps gives rise to an overall reaction equation. Hence, the reaction equation as follows,
The overall equation becomes,
In the reaction, the slow step is the rate determining step; and its rate law is the overall rate law.
Therefore, the rate law of the slow step is,
The concentration
The rate law for the given mechanism steps are,
The rate of mechanism (1),
Thus, by substituting above relation into the equation (1), the rate law becomes,
Therefore, the given rate law is consistent with the rate law of overall reaction obtained as above.
Therefore, all the mechanisms are consistent with the rate law.
(b)
Interpretation:
Among the given experiments the one that is most reasonable has to be predicted.
Concept introduction:
Rate law or rate equation: The relationship between the reactant concentrations and reaction rate is expressed by an equation.
Order of a reaction: The order of a reaction with respect to a particular reactant is the exponent of its concentration term in the rate law expression, and the overall reaction order is the sum of the exponents on all concentration terms.
Rate constant, k: It is a proportionality constant that relates rate and concentration at a given temperature.
(b)

Explanation of Solution
- Experiment (1):
The given reaction is one-step collision, hence the reaction equation becomes,
- Experiment (2):
The given reaction involves multiple mechanism steps, by adding the entire individual steps gives rise to an overall reaction equation. Hence, the reaction equation as follows,
The overall equation becomes,
- Experiment (3):
The given reaction involves multiple mechanism steps, by adding the entire individual steps gives rise to an overall reaction equation. Hence, the reaction equation as follows,
The overall equation becomes,
Comparing all the experiments, the experiment (1) and (3) are termolecular molecularity; and the experiment (2) is bimolecular. Since, the most reasonable mechanism is (2).
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Chapter 16 Solutions
Chemistry: The Molecular Nature of Matter and Change
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