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Chapter 14: Problem 46

If even a tiny spark is introduced into a mixture of \(\mathrm{H}_{2}(\mathrm{g})\) and \(\mathrm{O}_{2}(\mathrm{g}),\) a highly exothermic explosive reaction occurs. Without the spark, the mixture remains unreacted indefinitely. (a) Explain this difference in behavior. (b) Why is the nature of the reaction independent of the size of the spark?

Short Answer

Expert verified
The mixture of hydrogen and oxygen gas doesn't explode on its own due to the absence of the required activation energy needed to overcome the energy barrier and break the molecular bonds. The introduction of a spark provides this necessary activation energy, leading to an explosive chain reaction. Regardless of the spark's size, as long as it provides the minimum activation energy, the nature of the reaction remains the same because the spark only initiates the reaction, which then becomes self-sustaining.

Step by step solution

01

Understanding the concept of activation energy and its role in the reaction

Activation energy can be defined as the least amount of energy needed to initiate a chemical reaction. In the case of the mixture of hydrogen gas (\(\mathrm{H}_{2}(\mathrm{g})\)) and oxygen gas (\(\mathrm{O}_{2}(\mathrm{g})\)), the activation energy barrier is relatively high. In the absence of the spark, the system lacks the energy needed to break the bonds of the reactant molecules and hence, is unable to reach the transition state, leading to no reaction.
02

Explaining the impact of the spark on the reaction

When a spark is introduced to the gaseous mixture, it provides the required activation energy needed to overcome the energy barrier. It helps to break the bonds in the hydrogen and oxygen molecules and creates free radicals which react with more hydrogen and oxygen molecules, leading to a chain reaction. This chain reaction results in the explosive reaction observed.
03

Discussing the influence of the size of the spark

The size or intensity of the spark does not affect the nature of the reaction because all it does is provide the initial activation energy needed to cross the energy barrier. As long as this minimum energy requirement is met, irrespective of how much bigger the spark is, the reaction will proceed the same way. The spark's role is to initiate the reaction, and thereafter, the reaction becomes self-sustaining due to the production of free radicals.

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Most popular questions from this chapter

The reaction \(A+B \longrightarrow\) products is first order in \(A\) first order in \(\mathrm{B},\) and second order overall. Consider that the starting concentrations of the reactants are \([\mathrm{A}]_{0}\) and [ \(\mathrm{B}]_{0},\) and that \(x\) represents the decrease in these concentrations at the time \(t .\) That is, \([\mathrm{A}]_{t}=[\mathrm{A}]_{0}-x\) and \([\mathrm{B}]_{t}=[\mathrm{B}]_{0}-x .\) Show that the integrated rate law for this reaction can be expressed as shown below. $$\ln \frac{[\mathrm{A}]_{0} \times[\mathrm{B}]_{t}}{[\mathrm{B}]_{0} \times[\mathrm{A}]_{t}}=\left([\mathrm{B}]_{0}-[\mathrm{A}]_{0}\right) \times k t$$

For the reaction \(A \longrightarrow\) products the following data are obtained. $$\begin{array}{cll} \hline {\text { Experiment 1 }} & &{\text { Experiment 2 }} \\ \hline [\mathrm{A}]=1.204 \mathrm{M} & t=0 \mathrm{min} & {[\mathrm{A}]=2.408 \mathrm{M}} & t=0 \mathrm{min}\\\ {[\mathrm{A}]=1.180 \mathrm{M}} & t=1.0 \mathrm{min} & {[\mathrm{A}]=?} & t=1.0 \mathrm{min} \\ {[\mathrm{A}]=0.602 \mathrm{M}} & t=35 \mathrm{min} & {[\mathrm{A}]=?} & t=30 \mathrm{min} \\ \hline \end{array}$$ (a) Determine the initial rate of reaction in Experiment 1. (b) If the reaction is second order, what will be \([\mathrm{A}]\) at \(t=1.0\) min in Experiment 2? (c) If the reaction is first order, what will be \([\mathrm{A}]\) at 30 min in Experiment 2?

A reaction is \(50 \%\) complete in 30.0 min. How long after its start will the reaction be \(75 \%\) complete if it is (a) first order; (b) zero order?

The object is to study the kinetics of the reaction between peroxodisulfate and iodide ions. $$\begin{aligned} &\text { (a) } \mathrm{S}_{2} \mathrm{O}_{8}^{2-}(\mathrm{aq})+3 \mathrm{I}^{-}(\mathrm{aq}) \longrightarrow 2 \mathrm{SO}_{4}^{2-}(\mathrm{aq})+\mathrm{I}_{3}^{-}(\mathrm{aq}) \end{aligned}$$ The \(I_{3}^{-}\) formed in reaction (a) is actually a complex of iodine, \(\mathrm{I}_{2},\) and iodide ion, \(\mathrm{I}^{-}\). Thiosulfate ion, \(\mathrm{S}_{2} \mathrm{O}_{3}^{2-}\) also present in the reaction mixture, reacts with \(\mathrm{I}_{3}^{-}\) just as fast as it is formed. $$\text { (b) } 2 \mathrm{S}_{2} \mathrm{O}_{3}^{2-}(\mathrm{aq})+\mathrm{I}_{3}^{-}(\mathrm{aq}) \longrightarrow \mathrm{S}_{4} \mathrm{O}_{6}^{2-}+3 \mathrm{I}^{-}(\mathrm{aq})$$ When all of the thiosulfate ion present initially has been consumed by reaction (b), a third reaction occurs between \(\mathrm{I}_{3}^{-}(\mathrm{aq})\) and starch, which is also present in the reaction mixture. $$\text { (c) } \mathrm{I}_{3}^{-}(\mathrm{aq})+\operatorname{starch} \longrightarrow \text { blue complex }$$ The rate of reaction (a) is inversely related to the time required for the blue color of the starch-iodine complex to appear. That is, the faster reaction (a) proceeds, the more quickly the thiosulfate ion is consumed in reaction (b), and the sooner the blue color appears in reaction (c). One of the photographs shows the initial colorless solution and an electronic timer set at \(t=0 ;\) the other photograph shows the very first appearance of the blue complex (after 49.89 s). Tables I and II list some actual student data obtained in this study. $$\begin{array}{l} \hline\text { TABLE I } \\ \text { Reaction conditions at } 24^{\circ} \mathrm{C}: 25.0 \mathrm{mL} \text { of the } \\ \left(\mathrm{NH}_{4}\right)_{2} \mathrm{S}_{2} \mathrm{O}_{8}(\text { aq) listed, } 25.0 \mathrm{mL} \text { of the } \mathrm{KI}(\mathrm{aq}) \\ \text { listed, } 10.0 \mathrm{mL} \text { of } 0.010 \mathrm{M} \mathrm{Na}_{2} \mathrm{S}_{2} \mathrm{O}_{3}(\mathrm{aq}), \text { and } 5.0 \mathrm{mL} \\ \text { starch solution are mixed. The time is that of the } \\ \text { first appearance of the starch-iodine complex. } \\ \hline & \text { Initial Concentrations, } \mathrm{M} \\ \hline \text { Experiment } & \left(\mathrm{NH}_{4}\right)_{2} \mathrm{S}_{2} \mathrm{O}_{8} & \mathrm{KI} & \text { Time, s } \\ \hline 1 & 0.20 & 0.20 & 21 \\ 2 & 0.10 & 0.20 & 42 \\ 3 & 0.050 & 0.20 & 81 \\ 4 & 0.20 & 0.10 & 42 \\ 5 & 0.20 & 0.050 & 79 \\ \hline \end{array}$$ $$\begin{array}{l} \hline \text { TABLE II } \\ \text { Reaction conditions: those listed in Table I for } \\ \text { Experiment } 4, \text { but at the temperatures listed. } \\ \hline \text { Experiment } & \text { Temperature, }^{\circ} \mathrm{C} & \text { Time, } \mathrm{s} \\ \hline 6 & 3 & 189 \\ 7 & 13 & 88 \\ 8 & 24 & 42 \\ 9 & 33 & 21 \\ \hline \end{array}$$ (a) Use the data in Table I to establish the order of reaction (a) with respect to \(\mathrm{S}_{2} \mathrm{O}_{8}^{2-}\) and to I \(^{-}\). What is the overall reaction order? [Hint: How are the times required for the blue complex to appear related to the actual rates of reaction? (b) Calculate the initial rate of reaction in Experiment 1 expressed in \(\mathrm{M} \mathrm{s}^{-1} .\) [Hint: You must take into account the dilution that occurs when the various solutions are mixed, as well as the reaction stoichiometry indicated by equations \((a),(b), \text { and }(c) .]\) (c) Calculate the value of the rate constant, \(k,\) based on experiments 1 and 2 (d) Calculate the rate constant, \(k\), for the four different temperatures in Table II. (e) Determine the activation energy, \(E_{\mathrm{a}}\), of the peroxodisulfate- iodide ion reaction. (f) The following mechanism has been proposed for reaction (a). The first step is slow, and the others are fast. $$\begin{array}{c} \mathrm{I}^{-}+\mathrm{S}_{2} \mathrm{O}_{8}^{2-} \longrightarrow \mathrm{IS}_{2} \mathrm{O}_{8}^{3-} \\ \mathrm{IS}_{2} \mathrm{O}_{8}^{3-} \longrightarrow 2 \mathrm{SO}_{4}^{2-}+\mathrm{I}^{+} \\ \mathrm{I}^{+}+\mathrm{I}^{-} \longrightarrow \mathrm{I}_{2} \\ \mathrm{I}_{2}+\mathrm{I}^{-} \longrightarrow \mathrm{I}_{3}^{-} \end{array}$$ Show that this mechanism is consistent with both the stoichiometry and the rate law of reaction (a). Explain why it is reasonable to expect the first step in the mechanism to be slower than the others.

The reaction \(A \longrightarrow\) products is first order in A. (a) If \(1.60 \mathrm{g} \mathrm{A}\) is allowed to decompose for 38 min, the mass of A remaining undecomposed is found to be 0.40 g. What is the half-life, \(t_{1 / 2}\), of this reaction? (b) Starting with \(1.60 \mathrm{g} \mathrm{A},\) what is the mass of \(\mathrm{A}\) remaining undecomposed after \(1.00 \mathrm{h} ?\)
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