Chapter 14: Problem 83
Explain why rate laws generally cannot be written from balanced equations. Under what circumstance is the rate law related directly to the balanced equation for a reaction?
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Chapter 14: Problem 83
Explain why rate laws generally cannot be written from balanced equations. Under what circumstance is the rate law related directly to the balanced equation for a reaction?
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(a) Two reactions have identical values for \(E_{a}\). Does this ensure that they will have the same rate constant if run at the same temperature? Explain. (b) Two similar reactions have the same rate constant at \(25^{\circ} \mathrm{C}\), but at \(35^{\circ} \mathrm{C}\) one of the reactions has a higher rate constant than the other. Account for these observations.
What is the molecularity of each of the following elementary reactions? Write the rate law for each. (a) \(\mathrm{Cl}_{2}(g) \rightarrow 2 \mathrm{Cl}(g)\) (b) \(\mathrm{OCl}^{-}(a q)+\mathrm{H}_{2} \mathrm{O}(l) \rightarrow \mathrm{HOCl}(a q)+\mathrm{OH}^{-}(a q)\) (c) \(\mathrm{NO}(g)+\mathrm{Cl}_{2}(g) \longrightarrow \mathrm{NOCl}_{2}(g)\)
As described in Exercise \(14.37\), the decomposition of sulfuryl chloride \(\left(\mathrm{SO}_{2} \mathrm{Cl}_{2}\right)\) is a first-order process. The rate constant for the decomposition at \(660 \mathrm{~K}\) is \(4.5 \times 10^{-2} \mathrm{~s}^{-1}\). (a) If we begin with an initial \(\mathrm{SO}_{2} \mathrm{Cl}_{2}\) pressure of 375 torr, what is the pressure of this substance after 65 s? (b) At what time will the pressure of \(\mathrm{SO}_{2} \mathrm{Cl}_{2}\) decline to one-tenth its initial value?
The rates of many atmospheric reactions are accelerated by the absorption of light by one of the reactants. For example, consider the reaction between methane and chlorine to produce methyl chloride and hydrogen chloride: Reaction 1: \(\mathrm{CH}_{4}(\mathrm{~g})+\mathrm{Cl}_{2}(\mathrm{~g}) \longrightarrow \mathrm{CH}_{3} \mathrm{Cl}(\mathrm{g})+\mathrm{HCl}(\mathrm{g})\) This reaction is very slow in the absence of light. However, \(\mathrm{Cl}_{2}(g)\) can absorb light to form \(\mathrm{Cl}\) atoms: $$ \text { Reaction 2: } \mathrm{Cl}_{2}(g)+h v \longrightarrow 2 \mathrm{Cl}(g) $$ Once the \(\mathrm{Cl}\) atoms are generated, they can catalyze the reaction of \(\mathrm{CH}_{4}\) and \(\mathrm{Cl}_{2}\), according to the following proposed mechanism: Reaction 3: \(\mathrm{CH}_{4}(\mathrm{~g})+\mathrm{Cl}(\mathrm{g}) \longrightarrow \mathrm{CH}_{3}(\mathrm{~g})+\mathrm{HCl}(\mathrm{g})\) Reaction 4: \(\mathrm{CH}_{3}(\mathrm{~g})+\mathrm{Cl}_{2}(g) \longrightarrow \mathrm{CH}_{3} \mathrm{Cl}(g)+\mathrm{Cl}(g)\) The enthalpy changes and activation energies for these two reactions are tabulated as follows: $$ \begin{array}{lll} \hline \text { Reaction } & \Delta H_{\mathrm{ran}}^{\circ}(\mathrm{kJ} / \mathrm{mol}) & E_{a}(\mathrm{~kJ} / \mathrm{mol}) \\ \hline 3 & +4 & 17 \\ 4 & -109 & 4 \end{array} $$ (a) By using the bond enthalpy for \(\mathrm{Cl}_{2}\) (Table \(8.4\) ), determine the longest wavelength of light that is energetic enough to cause reaction 2 to occur. In which portion of the electromagnetic spectrum is this light found? (b) By using the data tabulated here, sketch a quantitative energy profile for the catalyzed reaction represented by reactions 3 and 4. (c) By using bond enthalpies, estimate where the reactants, \(\mathrm{CH}_{4}(g)+\mathrm{Cl}_{2}(g)\), should be placed on your diagram in part (b). Use this result to estimate the value of \(E_{a}\) for the reaction \(\mathrm{CH}_{4}(g)+\mathrm{Cl}_{2}(g) \longrightarrow\) \(\mathrm{CH}_{3}(g)+\mathrm{HCl}(g)+\mathrm{Cl}(g) .\) (d) The species \(\mathrm{Cl}(g)\) and \(\mathrm{CH}_{3}(\mathrm{~g})\) in reactions 3 and 4 are radicals, that is, atoms or molecules with unpaired electrons. Draw a Lewis structure of \(\mathrm{CH}_{3}\), and verify that is a radical. (e) The sequence of reactions 3 and 4 comprise a radical chain mechanism. Why do you think this is called a "chain reaction"? Propose a reaction that will terminate the chain reaction.
The rate of a first-order reaction is followed by spectroscopy, monitoring the absorption of a colored reactant. The reaction occurs in a \(1.00-\mathrm{cm}\) sample cell, and the only colored species in the reaction has a molar absorptivity constant of \(5.60 \times 10^{3} \mathrm{~cm}^{-1} \mathrm{M}^{-1}\). (a) Calculate the initial concentration of the colored reactant if the absorbance is \(0.605\) at the beginning of the reaction. (b) The absorbance falls to \(0.250\) within \(30.0\) min. Calculate the rate constant in units of \(\mathrm{s}^{-1}\). (c) Calculate the half-life of the reaction. (d) How long does it take for the absorbance to fall to \(0.100 ?\)
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