Chapter 16: Q16.9 P (page 728)
Give two reasons to measure initialrates in a kinetic study.
The answer is,
1) To calculate the overall rate of a reaction.
2) To calculate many other kinetic parameters.
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For the reaction , how many unique collisions between A and B are possible if 1.01 mol of A(g) and 2.12 mol of B(g) are present in the vessel?
Even when a mechanism is consistent with the rate law, later work may show it to be incorrect. For example, the reaction between hydrogen and iodine has this rate law: . The long-accepted mechanism had a single bimolecular step; that is, the overall reaction was thought to be elementary:
In the 1960s, however, spectroscopic evidence showed the presence of free I atoms during the reaction. Kineticists have since proposed a three-step mechanism:
Show that this mechanism is consistent with the rate law.
To determine its rate law. Assuming that you have a valid experimental procedure for obtaining [A2] and [B2] at various times, explain how you determine
(a) the initial rate,
(b) the reaction orders, and
(c) the rate constant.
Iodide ion reacts with chloromethane to displace chloride ion in a common organic substitution reaction:
(a) Draw a wedge-bond structure of chloroform and indicate the most effective direction of attack.
(b) The analogous reaction with 2-chlorobutane [Figure P16.107(b)] results in a major change in specific rotation as measured by polarimetry. Explain, showing a wedge-bond structure of the product.
(c) Under different conditions, 2-chlorobutane loses in a rate-determining step to form a planar intermediate [Figure P16.107(c)]. This cationic species reacts with HI and then loses H to form a product that exhibits no optical activity. Explain, showing a wedge-bond structure.
If the temperature in Problem 16.60 is increased to , by what factor does the fraction of collisions with energy equal to or greater than the activation energy change?
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