A. The gas-phase homogeneous oxidation of nitrogen monoxide (NO) to dioxide (NO2),
2NO + O2→ 2NO2

is known to have a form of third-order kinetics, which suggests that the reaction is elementary as written, at least for low partial pressures of the nitrogen oxides. However, the rate constant k actually decreases with increasing absolute temperature, indicating an apparently negative activation energy. Because the activation energy of any elementary reaction must be positive, some explanation is in order. Provide an explanation, starting from the fact that an active intermediate species, NO3, is a participant in some other known reactions that involve oxides of nitrogen. Draw the reaction pathway.

b. The rate law for formation of phosgene, COC12, from chlorine, C12, and carbon monoxide, CO, has the rate law.

rCOCl2= k Cco C3/2. Cl2

Suggest a mechanism for this reaction that is consistent with this rate law and draw the reaction pathway. (Hint: Cl formed from the dissociation of C12 is one of the two active intermediates.)
c. List ways you can work this problem incorrectly.
d. How could you make this problem more difficult?

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most historians agree that gabriel mouton, the vicar of st. paul’s church in lyons, france, is the “founding father” of the metric system. he proposed a decimal system of measurement in 1670. mouton based it on the length of one minute of arc of a great circle of the earth (now called a nautical mile, 1852 meters). he also proposed the swing-length of a pendulum with a frequency of one beat per second as the unit of length (about 25 cm). a pendulum beating with this length would have been fairly easy to produce, thus facilitating the widespread distribution of uniform standards. over the years, his work was revised, improved, and extended by a number of french scientists.

the political sponsor of weights and measures reform in the french revolutionary national assembly was the bishop of autun, better known as talleyrand. under his auspices, the french academy appointed several committees to carry out the work of developing a usable system of weights and measures for france. one of the committees recommended a decimalized measurement system based upon a length equal to one ten-millionth of the length of a quadrant of the earth’s meridian (i.e., one ten-millionth of the distance between the equator and the north pole).