Chapter 14: Problem 79
(a) Explain the importance of enzymes in biological systems. (b) What chemical transformations are catalyzed (i) by the enzyme catalase, (ii) by nitrogenase?
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Chapter 14: Problem 79
(a) Explain the importance of enzymes in biological systems. (b) What chemical transformations are catalyzed (i) by the enzyme catalase, (ii) by nitrogenase?
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The isomerization of methyl isonitrile \(\left(\mathrm{CH}_{3} \mathrm{NC}\right)\) to acetonitrile \(\left(\mathrm{CH}_{3} \mathrm{CN}\right)\) was studied in the gas phase at \(215^{\circ} \mathrm{C}\), and the following data were obtained: $$ \begin{array}{ll} \hline \text { Time (s) } & \text { [CH }_{3} \text { NC] (M) } \\ \hline 0 & 0.0165 \\ 2,000 & 0.0110 \\ 5,000 & 0.00591 \\ 8,000 & 0.00314 \\ 12,000 & 0.00137 \\ 15,000 & 0.00074 \\ \hline \end{array} $$ (a) Calculate theaverage rate of reaction, in \(M / \mathrm{s}\), for the time interval between each measurement. (b) Graph \(\left[\mathrm{CH}_{3} \mathrm{NC}\right]\) versus time, and determine the instantaneous rates in \(\mathrm{M} / \mathrm{s}\) at \(t=5000 \mathrm{~s}\) and \(t=8000 \mathrm{~s}\).
There are literally thousands of enzymes at work in complex living systems such as human beings. What properties of the enzymes give rise to their ability to distinguish one substrate from another?
NO catalyzes the decomposition of \(\mathrm{N}_{2} \mathrm{O}\), possibly by the following mechanism: $$ \begin{array}{r} \mathrm{NO}(\mathrm{g})+\mathrm{N}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow \mathrm{N}_{2}(g)+\mathrm{NO}_{2}(g) \\ 2 \mathrm{NO}_{2}(g) \longrightarrow 2 \mathrm{NO}(g)+\mathrm{O}_{2}(g) \end{array} $$ (a) What is the chemical equation for the overall reaction? Show how the two steps can be added to give the overall equation. (b) Why is NO considered a catalyst and not an intermediate? (c) If experiments show that during the decomposition of \(\mathrm{N}_{2} \mathrm{O}, \mathrm{NO}_{2}\) does not accumulate in measurable quantities, does this rule out the proposed mechanism? If you think not, suggest what might be going on.
The rate of the reaction \(\mathrm{CH}_{3} \mathrm{COOC}_{2} \mathrm{H}_{5}(a q)+\mathrm{OH}^{-}(a q) \longrightarrow\) \(\mathrm{CH}_{3} \mathrm{COO}^{-}(a q)+\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}(a q)\) was measured at several temperatures, and the following data were collected: $$ \begin{array}{ll} \hline \text { Temperature }\left({ }^{\circ} \mathrm{C}\right) & k\left(\mathrm{M}^{-1} \mathrm{~s}^{-1}\right) \\ \hline 15 & 0.0521 \\ 25 & 0.101 \\ 35 & 0.184 \\ 45 & 0.332 \end{array} $$ Using these data, graph \(\ln k\) versus \(1 / T\). Using your graph, determine the value of \(E_{g}\)
Consider two reactions. Reaction (1) has a constant halflife, whereas reaction (2) has a half-life that gets longer as the reaction proceeds. What can you conclude about the rate laws of these reactions from these observations?
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