Chapter 14: Problem 75
(a) What is a catalyst? (b) What is the difference between a homogeneous and a heterogeneous catalyst? (c) Do catalysts affect the overall enthalpy change for a reaction, the activation energy, or both?
Chapter 14: Problem 75
(a) What is a catalyst? (b) What is the difference between a homogeneous and a heterogeneous catalyst? (c) Do catalysts affect the overall enthalpy change for a reaction, the activation energy, or both?
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Get started for freeAmericium-241 is used in smoke detectors. It has a first-order rate constant for radioactive decay of \(k=1.6 \times 10^{-3} \mathrm{yr}^{-1}\). By contrast, iodine-125, which is used to test for thyroid functioning, has a rate constant for radioactive decay of \(k=0.011\) day \(^{-1}\). (a) What are the half-lives of these two isotopes? (b) Which one decays at a faster rate? (c) How much of a \(1.00\)-mg sample of each isotope remains after 3 half-lives? (d) How much of a 1.00-mg sample of each isotope remains after 4 days?
For each of the following gas-phase reactions, write the rate expression in terms of the appearance of each product and disappearance of each reactant: (a) \(2 \mathrm{H}_{2} \mathrm{O}(g) \longrightarrow 2 \mathrm{H}_{2}(g)+\mathrm{O}_{2}(g)\) (b) \(2 \mathrm{SO}_{2}(g)+\mathrm{O}_{2}(g) \longrightarrow 2 \mathrm{SO}_{3}(g)\) (c) \(2 \mathrm{NO}(g)+2 \mathrm{H}_{2}(g) \longrightarrow \mathrm{N}_{2}(g)+2 \mathrm{H}_{2} \mathrm{O}(g)\) (d) \(\mathrm{N}_{2}(g)+2 \mathrm{H}_{2}(g) \longrightarrow \mathrm{N}_{2} \mathrm{H}_{4}(g)\)
Cyclopentadiene \(\left(\mathrm{C}_{5} \mathrm{H}_{6}\right)\) reacts with itself to form dicyclopentadiene $\left(\mathrm{C}_{10} \mathrm{H}_{12}\right)\(. A \)0.0400 \mathrm{M}\( solution of \)\mathrm{C}_{5} \mathrm{H}_{6}$ was monitored as a function of time as the reaction $2 \mathrm{C}_{5} \mathrm{H}_{6} \longrightarrow \mathrm{C}_{10} \mathrm{H}_{12}$ proceeded. The following data were collected: $$ \begin{array}{cc} \hline \text { Time (s) } & {\left[\mathrm{C}_{5} \mathrm{H}_{6}\right](M)} \\\ \hline 0.0 & 0.0400 \\ 50.0 & 0.0300 \\ 100.0 & 0.0240 \\ 150.0 & 0.0200 \\ 200.0 & 0.0174 \\ \hline \end{array} $$ Plot \(\left[\mathrm{C}_{5} \mathrm{H}_{6}\right]\) versus time, $\ln \left[\mathrm{C}_{5} \mathrm{H}_{6}\right]\( versus time, and \)1 /\left[\mathrm{C}_{5} \mathrm{H}_{6}\right]$ versus time. (a) What is the order of the reaction? (b) What is the value of the rate constant?
Platinum nanoparticles of diameter \(\sim 2 \mathrm{~nm}\) are important catalysts in carbon monoxide oxidation to carbon dioxide. Platinum crystallizes in a face-centered cubic arrangement with an edge length of \(3.924 \AA\). (a) Estimate how many platinum atoms would fit into a \(2.0-\mathrm{nm}\) sphere; the volume of a sphere is \((4 / 3) \pi r^{3}\). Recall that \(1 \dot{A}=1 \times 10^{-10} \mathrm{~m}\) and \(1 \mathrm{~nm}=1 \times 10^{-9} \mathrm{~m}\). (b) Estimate how many platinum atoms are on the surface of a \(2.0\)-nm Pt sphere, using the surface area of a sphere \(\left(4 \pi r^{2}\right)\) and assuming that the "footprint" of one Pt atom can be estimated from its atomic diameter of \(2.8 \mathrm{~A}\). (c) Using your results from (a) and (b), calculate the percentage of \(\mathrm{Pt}\) atoms that are on the surface of a \(2.0-\mathrm{nm}\) nanoparticle. (d) Repeat these calculations for a \(5.0\)-nm platinum nanoparticle. (e) Which size of nanoparticle would you expect to be more catalytically active and why?
The following is a quote from an article in the August 18, 1998 , issue of The New York Times about the breakdown of cellulose and starch: "A drop of 18 degrees Fahrenheit [from \(77^{\circ} \mathrm{F}\) to \(59^{\circ} \mathrm{F}\) ] lowers the reaction rate six times; a 36-degree drop [from \(77^{\circ} \mathrm{F}\) to \(41^{\circ} \mathrm{F}\) ] produces a fortyfold decrease in the rate." (a) Calculate activation energies for the breakdown process based on the two estimates of the effect of temperature on rate. Are the values consistent? (b) Assuming the value of \(E_{a}\) calculated from the \(36^{\circ}\) drop and that the rate of breakdown is first order with a half-life at \(25^{\circ} \mathrm{C}\) of \(2.7 \mathrm{yr}\), calculate the half-life for breakdown at a temperature of \(-15^{\circ} \mathrm{C}\).
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