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Chapter 14: Problem 110

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?

Short Answer

Expert verified
(a) The initial rate of reaction is 0.024 M/min. (b) If the reaction is second order, [A] at t=1.0 min in Experiment 2 is approximately 0.962 M. (c) If the reaction is first order, [A] at t=30 min in Experiment 2 is approximately 3.215 M.

Step by step solution

01

Determine the initial rate of reaction

From the data given, at \(t=0\) min, we have \([A]=1.204\) M and at \(t=1.0\) min, \([A]=1.180\) M. The rate of reaction is defined as the change in concentration of reactant A over the change in time. So, \(Rate=-\Delta[A]/\Delta t\). Substituting the values in, we have \(- (1.180-1.204)/(1.0-0)\) which gives \(Rate = 0.024\) M/min.
02

Calculate [A] at t=1.0 min in Experiment 2 given a second order reaction

For a second order reaction, the rate law is \(\frac{1}{[A]_t}\) = \(\frac{1}{[A]_0}\) + kt. Using the rate calculated in step 1 as k, and considering the initial concentration of A in Experiment 2 as 2.408 M, we can calculate the concentration of A at 1.0 min. Rearranging the second order rate law gives \([A]_t = \frac{1} {\frac{1}{2.408} + 0.024*1}\), which evaluates to approximately 0.962 M.
03

Calculate [A] at t=30 min in Experiment 2 given a first order reaction

For a first order reaction, the rate law is \(\ln[A]_t = -kt + \ln[A]_0\). Using the rate calculated in step 1 as k, and the initial concentration of A in Experiment 2, we can calculate the concentration of A at 30 min. Substituting the values into the rate law gives \( \ln[A]_{30} = -0.024*30 + \ln[2.408]\), which evaluates to approximately 1.167. Exponentiating this value gives \([A]_{30} = e^{1.167}\), which evaluates to approximately 3.215 M.

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Most popular questions from this chapter

For the reaction \(\mathrm{A}+\mathrm{B} \longrightarrow 2 \mathrm{C},\) which proceeds by a single-step bimolecular elementary process, (a) \(t_{1 / 2}=0.693 / k ;\) (b) rate of appearance of C= - rate of disappearance of \(\mathrm{A} ;\) (c) rate of reaction = \(k[\mathrm{A}][\mathrm{B}] ;\) (d) \(\ln [A]_{t}=-k t+\ln [A]_{0}.\)

The half-life for the first-order decomposition of nitramide, \(\mathrm{NH}_{2} \mathrm{NO}_{2}(\mathrm{aq}) \longrightarrow \mathrm{N}_{2} \mathrm{O}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(1),\) is \(123 \min\) at \(15^{\circ} \mathrm{C} .\) If \(165 \mathrm{mL}\) of a \(0.105 \mathrm{M} \mathrm{NH}_{2} \mathrm{NO}_{2}\) solution is allowed to decompose, how long must the reaction proceed to yield \(50.0 \mathrm{mL}\) of \(\mathrm{N}_{2} \mathrm{O}(\mathrm{g})\) collected over water at \(15^{\circ} \mathrm{C}\) and a barometric pressure of \(756 \mathrm{mm} \mathrm{Hg} ?\) (The vapor pressure of water at \(15^{\circ} \mathrm{C}\) is \(12.8 \mathrm{mmHg} .)\)

In the reaction \(2 \mathrm{A}+\mathrm{B} \longrightarrow \mathrm{C}+3 \mathrm{D},\) reactant \(\mathrm{A}\) is found to disappear at the rate of \(6.2 \times 10^{-4} \mathrm{M} \mathrm{s}^{-1}.\) (a) What is the rate of reaction at this point? (b) What is the rate of disappearance of \(\mathrm{B}\) ? (c) What is the rate of formation of D?

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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