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What is the molecularity of each of the following elementary reactions? Write the rate law for each. (a) \(\mathrm{H}_{2} \mathrm{O}(l)+\mathrm{CN}^{-}(a q) \longrightarrow \mathrm{HCN}(a q)\) (b) \(\mathrm{CH}_{3} \mathrm{Cl}(\) solv \()+\mathrm{OH}^{-}(\) solv \() \longrightarrow \mathrm{CH}_{3} \mathrm{OH}(\) solv \()+\mathrm{Cl}^{-}(\) solv \()\) (c) \(\mathrm{N}_{2} \mathrm{O}_{4}(g) \rightarrow 2 \mathrm{NO}_{2}\)

Short Answer

Expert verified
(a) The molecularity of the reaction is 2 (bimolecular). The rate law is: \[Rate = k [\mathrm{H}_2 \mathrm{O}] [\mathrm{CN}^-]\] (b) The molecularity of the reaction is 2 (bimolecular). The rate law is: \[Rate = k [\mathrm{CH}_3 \mathrm{Cl}] [\mathrm{OH}^-]\] (c) The molecularity of the reaction is 1 (unimolecular). The rate law is: \[Rate = k [\mathrm{N}_2 \mathrm{O}_4]\]

Step by step solution

01

(a) Molecularity of Reaction 1

In this reaction, there are two reactants: H2O and CN. Hence, the molecularity of this elementary reaction is 2, making it a bimolecular reaction.
02

(a) Rate Law for Reaction 1

The rate law will be the rate constant (k) multiplied by the concentrations of the reactants, each raised to the power of their respective stoichiometric coefficients. Since this is an elementary reaction, the coefficients are equal to the number of molecules of each reactant involved in the reaction. In this case, the rate law becomes: \[Rate = k [\mathrm{H}_2 \mathrm{O}] [\mathrm{CN}^-]\]
03

(b) Molecularity of Reaction 2

In this reaction, there are two reactants: CH3Cl and OH-. Hence, the molecularity of this elementary reaction is 2, making it a bimolecular reaction.
04

(b) Rate Law for Reaction 2

Following the same reasoning as in Reaction 1, the rate law for Reaction 2 will be the rate constant (k) multiplied by the concentrations of the reactants, each raised to the power of their respective stoichiometric coefficients. In this case, the rate law becomes: \[Rate = k [\mathrm{CH}_3 \mathrm{Cl}] [\mathrm{OH}^-]\]
05

(c) Molecularity of Reaction 3

In this reaction, there is only one reactant: N2O4. Hence, the molecularity of this elementary reaction is 1, making it a unimolecular reaction.
06

(c) Rate Law for Reaction 3

Following the same reasoning as in the previous reactions, the rate law for Reaction 3 will be the rate constant (k) multiplied by the concentration of the reactant, raised to the power of its stoichiometric coefficient. In this case, the rate law becomes: \[Rate = k [\mathrm{N}_2 \mathrm{O}_4]\]

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Rate Law
When studying chemical reactions, the concept of a rate law is essential to understanding how reactions proceed over time. A rate law expresses the relationship between the reaction rate and the concentration of reactants. For elementary reactions, which are reactions that occur in a single step with a single transition state, the rate law can be directly determined from the stoichiometry of the reactants involved.
This means that for an elementary reaction where
  • one reactant transforms into products, the rate law will be: \[ \text{Rate} = k [\text{A}] \] where \( k \) is the rate constant and \([\text{A}]\) is the concentration of the reactant.
  • two reactants are involved, the rate law takes the form: \[ \text{Rate} = k [\text{A}][\text{B}] \] with each concentration raised to the power of its stoichiometric coefficient.
These laws help chemists predict the speed of chemical reactions and are crucial for control in industrial processes.
Elementary Reaction
An elementary reaction is a single-step process with no intermediates. In this direct process, reactants proceed to form products without any recourse to more complicated mechanisms.
Elementary reactions are characterized by their simplicity and are used to understand more complex reaction mechanisms, as a complicated reaction can often be broken down into its elementary steps. It's important to remember that because they occur in a single step, the molecularity of an elementary reaction, which indicates the number of molecules colliding in the transition state, directly informs its rate law.
For instance, if two molecules collide and react, forming products immediately, it’s considered to be a bimolecular elementary reaction. This direct relationship allows chemists to form accurate rate equations based solely on stoichiometry, simplifying many calculations and interpretations of reaction kinetics.
Bimolecular Reaction
Bimolecular reactions involve two reactant molecules coming together to form products. In the context of elementary reactions, these occur in a single concerted step without any intermediate species.
The hallmark of a bimolecular reaction is that two species are involved in the crucial transition state – meaning both influence the rate of the reaction. The molecularity, in this case, is two, referring to the two entities colliding.
  • The typical rate law for a bimolecular reaction is: \[ \text{Rate} = k [\text{Reactant1}][\text{Reactant2}] \]
Each reactant concentration is raised to the power of one, reflecting the actual number of molecules required to trigger the reaction. Bimolecular reactions are quite common and can describe many everyday chemical processes, from enzyme catalysis in biology to synthetic reactions in industrial chemistry.
Unimolecular Reaction
Unimolecular reactions are reactions where a single molecule undergoes change to form products. For these elementary reactions, the transformation is dependent on the concentration of just one reactant entity.
In a unimolecular process, the molecule might rearrange itself, break apart, or undergo some isomerization without the need for a second molecule to initiate the transformation. Such reactions are often preceded by some form of internal energy absorption, like heat or light, which prompts the molecule to surpass its energy barrier and proceed to products.
The rate law for a unimolecular reaction is straightforward:
  • \[ \text{Rate} = k [\text{Reactant}] \]
This simplicity, reflecting direct dependence on a single reactant, allows for easier analysis and prediction of reaction kinetics, making unimolecular reactions essential in fields such as gas-phase chemistry and photochemistry.

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Most popular questions from this chapter

(a) The gas-phase decomposition of sulfuryl chloride \(\left(\mathrm{SO}_{2} \mathrm{Cl}_{2}\right), \mathrm{SO}_{2} \mathrm{Cl}_{2}(g) \longrightarrow \mathrm{SO}_{2}(g)+\mathrm{Cl}_{2}(g)\) is first order in \(\mathrm{SO}_{2} \mathrm{Cl}_{2}\). At \(300^{\circ} \mathrm{C}\) the half-life for this process is two and a half days. What is the rate constant at this temperature? (b) At \(400^{\circ} \mathrm{C}\) the rate constant is \(0.19 \mathrm{~min}^{-1}\). What is the half-life at this temperature?

The following mechanism has been proposed for the gasphase reaction of \(\mathrm{H}_{2}\) with ICl: $$ \begin{array}{l} \mathrm{H}_{2}(g)+\mathrm{ICl}(g) \longrightarrow \mathrm{HI}(g)+\mathrm{HCl}(g) \\ \mathrm{HI}(g)+\mathrm{ICl}(g) \longrightarrow \mathrm{I}_{2}(g)+\mathrm{HCl}(g) \end{array} $$ (a) Write the balanced equation for the overall reaction. (b) Identify any intermediates in the mechanism. (c) If the first step is slow and the second one is fast, which rate law do you expect to be observed for the overall reaction?

For the elementary process \(\mathrm{N}_{2} \mathrm{O}_{5}(g) \longrightarrow \mathrm{NO}_{2}(g)+\mathrm{NO}_{3}(g)\) the activation energy \(\left(E_{a}\right)\) and overall \(\Delta E\) are \(154 \mathrm{~kJ} / \mathrm{mol}\) and \(136 \mathrm{~kJ} / \mathrm{mol}\), respectively. (a) Sketch the energy profile for this reaction, and label \(E_{a}\) and \(\Delta E\). (b) What is the activation energy for the reverse reaction?

The decomposition of hydrogen peroxide is catalyzed by iodide ion. The catalyzed reaction is thought to proceed by a two-step mechanism: $$ \begin{aligned} \mathrm{H}_{2} \mathrm{O}_{2}(a q)+\mathrm{I}^{-}(a q) & \longrightarrow \mathrm{H}_{2} \mathrm{O}(l)+\mathrm{IO}^{-}(a q)(\text { slow }) \\ \mathrm{IO}^{-}(a q)+\mathrm{H}_{2} \mathrm{O}_{2}(a q) & \longrightarrow \mathrm{H}_{2} \mathrm{O}(l)+\mathrm{O}_{2}(g)+\mathrm{I}^{-}(a q) \quad(\text { fast }) \end{aligned} $$ (a) Write the chemical equation for the overall process. (b) Identify the intermediate, if any, in the mechanism. (c) Assuming that the first step of the mechanism is rate determining, predict the rate law for the overall process.

The enzyme urease catalyzes the reaction of urea, \(\left(\mathrm{NH}_{2} \mathrm{CONH}_{2}\right)\), with water to produce carbon dioxide and ammonia. In water, without the enzyme, the reaction proceeds with a first-order rate constant of \(4.15 \times 10^{-5} \mathrm{~s}^{-1}\) at \(100^{\circ} \mathrm{C}\). In the presence of the enzyme in water, the reaction proceeds with a rate constant of \(3.4 \times 10^{4} \mathrm{~s}^{-1}\) at \(21^{\circ} \mathrm{C}\). (a) Write out the balanced equation for the reaction catalyzed by urease. \((\mathbf{b})\) If the rate of the catalyzed reaction were the same at \(100^{\circ} \mathrm{C}\) as it is at \(21^{\circ} \mathrm{C}\), what would be the difference in the activation energy between the catalyzed and uncatalyzed reactions? (c) In actuality, what would you expect for the rate of the catalyzed reaction at \(100^{\circ} \mathrm{C}\) as compared to that at \(21^{\circ} \mathrm{C} ?(\mathbf{d})\) On the basis of parts (c) and (d), what can you conclude about the difference in activation energies for the catalyzed and uncatalyzed reactions?

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