Write the rate expression for each of the following elementary steps: (a) \(\mathrm{NO}+\mathrm{O}_{3} \longrightarrow \mathrm{NO}_{2}+\mathrm{O}_{2}\) (b) \(2 \mathrm{NO}_{2} \longrightarrow 2 \mathrm{NO}+\mathrm{O}_{2}\) (c) \(\mathrm{K}+\mathrm{HCl} \longrightarrow \mathrm{KCl}+\mathrm{H}\)

Short Answer

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Question: Write the rate expression for each of the following elementary reactions: (a) NO + O3 → NO2 + O2 (b) 2NO2 → 2NO + O2 (c) K + HCl → KCl + H Answer: (a) Rate = k [NO][O3] (b) Rate = k [NO2]^2 (c) Rate = k [K][HCl]

Step by step solution

01

Reaction (a) - Identify Reactants and Molecularity

In the first reaction, we have \(\mathrm{NO}\) and \(\mathrm{O}_{3}\) as reactants. Each reactant has a molecularity of 1 because there is only one molecule involved in the reaction.
02

Reaction (a) - Write Rate Expression

For reaction (a), the rate expression is given by: $$ \text{Rate} = k [\mathrm{NO}]^1 [\mathrm{O}_{3}]^1 $$
03

Reaction (b) - Identify Reactants and Molecularity

In the second reaction, we have \(\mathrm{NO}_{2}\) as the reactant. It has a molecularity of 2 because there are two molecules involved in the reaction.
04

Reaction (b) - Write Rate Expression

For reaction (b), the rate expression is given by: $$ \text{Rate} = k [\mathrm{NO}_{2}]^2 $$
05

Reaction (c) - Identify Reactants and Molecularity

In the third reaction, we have \(\mathrm{K}\) and \(\mathrm{HCl}\) as reactants. Each reactant has a molecularity of 1 because there is only one molecule involved in the reaction.
06

Reaction (c) - Write Rate Expression

For reaction (c), the rate expression is given by: $$ \text{Rate} = k [\mathrm{K}]^1 [\mathrm{HCl}]^1 $$ To summarize, the rate expressions for the given elementary reactions are: (a) \(\text{Rate} = k [\mathrm{NO}] [\mathrm{O}_{3}]\) (b) \(\text{Rate} = k [\mathrm{NO}_{2}]^2\) (c) \(\text{Rate} = k [\mathrm{K}] [\mathrm{HCl}]\)

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Key Concepts

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

Chemical Kinetics
Chemical kinetics is an essential aspect of chemistry that studies the speed or rate at which a chemical reaction occurs and determines the factors influencing it. This field helps us understand how various conditions like temperature, concentration, and presence of catalysts can affect the rate of a reaction.

Understanding chemical kinetics allows us to predict how long it will take for a reaction to complete and what yield of products we can expect over time. It also plays a pivotal role in industries, where the efficiency of chemical processes can mean the difference between a profitable operation and a costly one.

When we talk about rate expressions, such as, \( \text{Rate} = k [\mathrm{NO}] [\mathrm{O}_{3}] \), the \(k\) in the equation represents the rate constant, which is specific to each reaction and can be influenced by external conditions. The rate constant is central to kinetical analyses, as it is a quantification of how fast the reaction proceeds under certain conditions.
Elementary Reaction Steps
Elementary reaction steps are the simplest reactions in which reactants convert to products in a single step and with a single transition state. These steps are crucial building blocks to understanding complex reactions, which happen in multiple stages.

An important feature of elementary reactions is how their rate expressions reflect the stoichiometry of the reactants involved. For example, the elementary reaction for the formation of \(\mathrm{NO}_{2}\) and \(\mathrm{O}_{2}\) from \(\mathrm{NO}\) and \(\mathrm{O}_{3}\) has a rate expression directly related to the concentrations of the reactants.

In a multi-step reaction, however, the overall rate expression can be more complex and is not always apparent from the stoichiometry of the overall reaction. Kinetic studies, often involving experiments, are utilized to determine the individual steps and their respective rate expressions.
Reaction Molecularity
Reaction molecularity refers to the number of reactant particles involved in an elementary reaction step. It is a key concept in understanding how reactants interact to form products.

Unimolecular and Bimolecular Reactions

Reactions can be classified as unimolecular or bimolecular. A unimolecular reaction involves a single molecule undergoing a transformation, while a bimolecular reaction involves two reactant molecules colliding and reacting together.

Using the reactions provided as examples, the conversion of \(\mathrm{NO}_{2}\) to \(\mathrm{NO}\) and \(\mathrm{O}_{2}\) in reaction (b) is a bimolecular step, as it involves two \(\mathrm{NO}_{2}\) molecules. The rate expression (\text{Rate} = k [\mathrm{NO}_{2}]^2) highlights this by squaring the concentration of \(\mathrm{NO}_{2}\).

Molecularity can also provide insights into the underlying reaction mechanism and is a fundamental concept that links the microscopic interactions of molecules to the macroscopic observable rate of a reaction.

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Most popular questions from this chapter

Ammonium cyanate, \(\mathrm{NH}_{4} \mathrm{NCO}\), in water rearranges to produce urea, a common fertilizer, \(\left(\mathrm{NH}_{2}\right)_{2} \mathrm{CO}\) : $$\mathrm{NH}_{4} \mathrm{NCO}(a q) \longrightarrow\left(\mathrm{NH}_{2}\right)_{2} \mathrm{CO}(a q)$$ The rearrangement is a second-order reaction. It takes \(11.6 \mathrm{~h}\) for the concentration of \(\mathrm{NH}_{4} \mathrm{NCO}\) to go from \(0.250 \mathrm{M}\) to \(0.0841 \mathrm{M}\). (a) What is \(k\) for the reaction? (b) What is the half-life of the reaction when \(\mathrm{NH}_{4} \mathrm{NCO}\) is \(0.100 \mathrm{M}\) ? (c) How long will it take to rearrange \(39 \%\) of a \(0.450 \mathrm{M}\) solution? (d) How fast is a \(0.839 \mathrm{M}\) solution being changed to urea?

A reaction has two reactants \(\mathrm{A}\) and \(\mathrm{B}\). What is the order with respect to each reactant and the overall order of the reaction described by each of the following rate expressions? (a) rate \(=k_{1}[\mathrm{~A}]^{3}\) (b) rate \(=k_{2}[\mathrm{~A}] \times[\mathrm{B}]\) (c) rate \(=k_{3}[\mathrm{~A}] \times[\mathrm{B}]^{2}\) (d) rate \(=k_{4}[\mathrm{~B}]\)

The reaction $$\mathrm{NO}(g)+\frac{1}{2} \mathrm{Br}_{2}(g) \longrightarrow \mathrm{NOBr}(g)$$ is second-order in nitrogen oxide and first-order in bromine. The rate of the reaction is \(1.6 \times 10^{-8} \mathrm{~mol} / \mathrm{L} \cdot \mathrm{min}\) when the nitrogen oxide concentration is \(0.020 \mathrm{M}\) and the bromine concentration is \(0.030 \mathrm{M}\). (a) What is the value of \(k\) ? (b) At what concentration of bromine is the rate \(3.5 \times 10^{-7} \mathrm{~mol} / \mathrm{L} \cdot \min\) and \([\mathrm{NO}]=0.043 \mathrm{M} ?\) (c) At what concentration of nitrogen oxide is the rate \(2.0 \times\) \(10^{-6} \mathrm{~mol} / \mathrm{L} \cdot \mathrm{min}\) and the bromine concentration one fourth of the nitrogen oxide concentration?

Experimental data are listed for the hypothetical reaction $$\mathrm{A}+\mathrm{B} \longrightarrow \mathrm{C}+\mathrm{D}$$ $$\begin{array}{lcccccc}\hline \text { Time (s) } & 0 & 10 & 20 & 30 & 40 & 50 \\\\{[\mathrm{~A}]} & 0.32 & 0.24 & 0.20 & 0.16 & 0.14 & 0.12 \\ \hline\end{array}$$ (a) Plot these data as in Figure \(11.2\). (b) Draw a tangent to the curve to find the instantaneous rate at \(30 \mathrm{~s}\). (c) Find the average rate over the 10 to \(40 \mathrm{~s}\) interval. (d) Compare the instantaneous rate at \(30 \mathrm{~s}\) with the average rate over the thirty-second interval.

The equation for the iodination of acetone in acidic solution is $$\mathrm{CH}_{3} \mathrm{COCH}_{3}(a q)+\mathrm{I}_{2}(a q) \longrightarrow \mathrm{CH}_{3} \mathrm{COCH}_{2} \mathrm{I}(a q)+\mathrm{H}^{+}(a q)+\mathrm{I}^{-}(a q)$$ The rate of the reaction is found to be dependent not only on the concentration of the reactants but also on the hydrogen ion concentration. Hence the rate expression of this reaction is $$\text { rate }=k\left[\mathrm{CH}_{3} \mathrm{COCH}_{3}\right]^{m}\left[\mathrm{I}_{2}\right]^{n}\left[\mathrm{H}^{+}\right]^{p}$$ The rate is obtained by following the disappearance of iodine using starch as an indicator. The following data are obtained: $$ \begin{array}{cccc} \hline\left[\mathrm{CH}_{3} \mathrm{COCH}_{3}\right] & \left.\mathrm{[H}^{+}\right] & {\left[\mathrm{I}_{2}\right]} & \text { Initial Rate }(\mathrm{mol} / \mathrm{L} \cdot \mathrm{s}) \\ \hline 0.80 & 0.20 & 0.001 & 4.2 \times 10^{-6} \\ 1.6 & 0.20 & 0.001 & 8.2 \times 10^{-6} \\ 0.80 & 0.40 & 0.001 & 8.7 \times 10^{-6} \\ 0.80 & 0.20 & 0.0005 & 4.3 \times 10^{-6} \\ \hline\end{array}$$ (a) What is the order of the reaction with respect to each reactant? (b) Write the rate expression for the reaction. (c) Calculate \(k\). (d) What is the rate of the reaction when \(\left[\mathrm{H}^{+}\right]=0.933 M\) and \(\left[\mathrm{CH}_{3} \mathrm{COCH}_{3}\right]=3\left[\mathrm{H}^{+}\right]=10\left[\mathrm{I}^{-}\right] ?\)

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