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3. Catalysts speed up the establishment of an equilibrium between starting materials and products. 4. Alkanes react with halogens (except iodine) by a radical chain mechanism to give haloalkanes. The mechanism consists of initiation to create a halogen atom, two propagation steps, and various termination steps. 5. In the first propagation step, the slower of the two, a hydrogen atom is abstracted from the alkane chain, a reaction resulting in an alkyl radical and HX. Hence, reactivity increases from I2 to F2. Selectivity decreases along the same series, as well as with increasing temperature. 6. The Hammond postulate states that fast, exothermic reactions are typically characterized by early transition states, which are similar in structure to the starting materials. On the other hand, slow, endothermic processes usually have late (productlike) transition states. 7. The DH 8 for a reaction may be calculated from the DH 8 values of the bonds affected in the process as follows: DH 8 5 S DH 8 bonds broken 2 S DH 8 bonds formed 8. The DH 8 for a radical halogenation process equals the sum of the DH 8 values for the propagation steps. 9. The relative reactivities of the various types of alkane C H bonds in halogenations can be estimated by factoring out statistical contributions. They are roughly constant under identical conditions and follow the order CH4 , Primary , CH Secondary , CH Tertiary CH

The reactivity differences between these types of CH bonds are greatest for bromination, making it the most selective radical halogenation process. Chlorination is much less selective, and fluorination shows very little selectivity. 10. The DH 8 of the combustion of an alkane is called the heat of combustion, DH 8 comb. The heats of combustion of isomeric compounds provide an experimental measure of their relative stabilities.

Problems
15. Label the primary, secondary, and tertiary hydrogens in each of the following compounds. CH3 CH3 (a) CH3CH2CH2CH3 (b) CH3CH2CH2CH2CH3 (c) (d)

16. Within each of the following sets of alkyl radicals, name each radical; identify each as either primary, secondary, or tertiary; rank in order of decreasing stability; and sketch an orbital picture of the most stable radical, showing the hyperconjugative interaction(s). . (a) CH3CH2CHCH3 and CH3CH2CH2CH2 ? . (b) (CH3CH2)2CHCH2 ? and (CH3CH2)2CCH3 . . (c) (CH3)2CHCHCH3, (CH3)2CCH2CH3, and (CH3)2CHCH2CH2? 17. Write as many products as you can think of that might result from the pyrolytic cracking of propane. Assume that the only initial process is C C bond cleavage. 18. Answer the question posed in Problem 17 for (a) butane and (b) 2-methylpropane. Use the data in Table 3-2 to determine the bond most likely to cleave homolytically, and use that bond cleavage as your first step. 19. Calculate DH 8 values for the following reactions. (a) H2 1 F2 -n 2 HF; (b) H2 1 Cl2 -n 2 HCl; (c) H2 1 Br2 -n 2 HBr; (d) H2 1 I2 -n 2 HI; (e) (CH3)3CH 1 F2 -n (CH3)3CF 1 HF; (f ) (CH3)3CH 1 Cl2 -n (CH3)3CCl 1 HCl; (g) (CH3)3CH 1 Br2 -n (CH3)3CBr 1 HBr; (h) (CH3)3CH 1 I2 -n (CH3)3CI 1 HI. 20. For each compound in Problem 15, determine how many constitutional isomers can form upon monohalogenation. (Hint: Identify all groups of hydrogens that reside in distinct structural environments in each molecule.)

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21. (a) Using the information given in Sections 3-6 and 3-7, write the products of the radical monochlorination of (i) pentane and (ii) 3-methylpentane. (b) For each, estimate the ratio of the isomeric monochlorination products that would form at 258C. (c) Using the bond strength data from Table 3-1, determine the DH 8 values of the propagation steps for the chlorination of 3-methylpentane at C3. What is the overall DH 8 value for this reaction? 22. Write in full the mechanism for monobromination of methane. Be sure to include initiation, propagation, and termination steps. 23. Sketch potential-energy/reaction-coordinate diagrams for the two propagation steps of the monobromination of methane (Problem 22). 24. Write a mechanism for the radical bromination of the hydrocarbon benzene, C6H6 (for structure, see Section 2-3). Use propagation steps similar to those in the halogenation of alkanes, as presented in Sections 3-4 through 3-6. Calculate DH 8 values for each step and for the reaction as a whole. How does this reaction compare thermodynamically with the bromination of other hydrocarbons? Data: DH 8 (C6H5 H) 5 112 kcal mol21; DH 8 (C6H5 Br) 5 81 kcal mol21. Note the Caution in Exercise 3-5. 25. Sketch potential-energy/reaction-coordinate diagrams for the two propagation steps of the monobromination of benzene (Problem 24). 26. Identify each of the diagrams you drew in Problem 25 as showing an early or a late transition state. 27. Write the major organic product(s), if any, of each of the following reactions. CH3 (a) CH3CH3 1 I2 CH3 (d) CH3CH CH2 CH3 CCH3 Cl2 CH3
hv

(b) CH3CH2CH3 1 F2 CH3 (e) CH3CH CH2 CH3 CCH3 Br2 CH3
hv

(c)

Br2

28. Calculate product ratios in each of the reactions in Problem 27. Use relative reactivity data for F2 and Cl2 at 258C and for Br2 at 1508C (Table 3-6). 29. Which, if any, of the reactions in Problem 27 give the major product with reasonable selectivity (i.e., are useful synthetic methods)? 30. (a) What would be the major organic product of monobromination of pentane at 1258C? (b) Draw Newman projections of all possible staggered conformations arising from rotation about the C2C3 bond for this product molecule. (c) Draw a qualitative graph of potential energy versus torsional angle for C2C3 rotation in this molecule. (Note: A bromine atom is considerably smaller, sterically, than is a methyl group.) 31. (a) Sketch a potential energy/reaction coordinate graph showing the two propagation steps for the monobromination of pentane to give the major product (Problem 30). Use DH 8 information from this chapter (Tables 3-1, 3-2, and 3-4, as appropriate). (b) Indicate the locations of the transition states and whether each is early or late. (c) Sketch a similar graph for reaction of pentane with I2. How does it differ from the graph for bromination? 32. At room temperature, 1,2-dibromoethane exists as an equilibrium mixture in which 89% of the molecules are in an anti conformation and 11% are gauche. The comparable ratio for butane under the same circumstances is 72% anti and 28% gauche. Suggest an explanation for the difference, bearing in mind that Br is sterically smaller than CH3 (see Problem 30). (Hint: Consider the polarity of a CBr bond and consequent electrostatic effects.) 33. Write balanced equations for the combustion of each of the following substances (molecular formulas may be obtained from Table 3-7): (a) methane; (b) propane; (c) cyclohexane; (d) ethanol; (e) sucrose. O O B B 34. Propanal (CH3CH2CH) and acetone (CH3CCH3) are isomers with the formula C3H6O. The heat of combustion of propanal is 2434.1 kcal mol21, that of acetone 2427.9 kcal mol21. (a) Write a

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balanced equation for the combustion of either compound. (b) What is the energy difference between propanal and acetone? Which has the lower energy content? (c) Which substance is more thermodynamically stable, propanal or acetone? (Hint: Draw a diagram similar to that in Figure 3-13.) 35. Sulfuryl chloride (SO2Cl2, see margin for structure) is a liquid reagent that may be used for chlorinations of alkanes as a substitute for gaseous elemental chlorine. Propose a mechanism for chlorination of CH4 using sulfuryl chloride. (Hint: Follow the usual model for a radical chain process, substituting SO2Cl2 for Cl2 where appropriate.) 36. Use the Arrhenius equation (Section 2-1) to estimate the ratio of the rate constants k for the reactions of a CH bond in methane with a chlorine atom and with a bromine atom at 258C. Assume that the A values for the two processes are equal, and use Ea 5 19 kcal mol21 for the reaction between Br ? and CH4. 37. When an alkane with different types of C H bonds, such as propane, reacts with an equimolar mixture of Br2 and Cl2, the selectivity in the formation of the brominated products is much worse than that observed when reaction is carried out with Br2 alone. (In fact, it is very similar to the selectivity for chlorination.) Explain. O Cl S O
Sulfuryl chloride
(b.p. 69C)

Cl

38. Bromination of 1-bromopropane gives the following results:

Br , 2008C

90%

8.5%

1.5%

Calculate the relative reactivities of the hydrogens on each of the three carbons toward bromine atoms. Compare these results with those from a simple alkane such as propane, and suggest explanations for any differences. 39. A hypothetical alternative mechanism for the halogenation of methane has the following propagation steps. (i) X ? 1 CH4 77777n CH3X 1 H ? (ii) H ? 1 X2 77777n HX 1 X? (a) Using DH 8 values from appropriate tables, calculate DH 8 for these steps for any one of the halogens. (b) Compare your DH 8 values with those for the accepted mechanism (Table 3-5). Do you expect this alternative mechanism to compete successfully with the accepted one? (Hint: Consider activation energies.) 40. The addition of certain materials called radical inhibitors to halogenation reactions causes the reactions to come to a virtually complete stop. An example is the inhibition by I2 of the chlorination of methane. Explain how this inhibition might come about. (Hint: Calculate DH 8 values for possible reactions of the various species present in the system with I2, and evaluate the possible further reactivity of the products of these I2 reactions.)

41. Typical hydrocarbon fuels (e.g., 2,2,4-trimethylpentane, a common component of gasoline) have very similar heats of combustion when calculated in kilocalories per gram. (a) Calculate heats of combustion per gram for several representative hydrocarbons in Table 3-7. (b) Make the same calculation for ethanol (Table 3-7). (c) In evaluating the feasibility of gasohol (90% gasoline and 10% ethanol) as a motor fuel, it has been estimated that an automobile running on pure ethanol would get approximately 40% fewer miles per gallon than would an identical automobile running on standard gasoline. Is this estimate consistent with the results in (a) and (b)? What can you say in general about the fuel capabilities of oxygen-containing molecules relative to hydrocarbons? 42. Two simple organic molecules that have been used as fuel additives are methanol (CH3OH) and 2-methoxy-2-methylpropane [tert-butyl methyl ether, (CH3)3COCH3]. The DH 8 comb values for these compounds in the gas phase are 2182.6 kcal mol21 for methanol and 2809.7 kcal mol21 for 2-methoxy-2-methylpropane. (a) Write balanced equations for the complete combustion of each of these molecules to CO2 and H2O. (b) Using Table 3-7, compare the DH 8 comb values for these compounds with those for alkanes with similar molecular weights. 43. Figure 3-9 compares the reactions of Cl ? with the primary and secondary hydrogens of propane. (a) Draw a similar diagram comparing the reactions of Br ? with the primary and secondary hydrogens of propane. (Hint: First obtain the necessary DH 8 values from Table 3-1 and calculate DH 8 for both the primary and the secondary hydrogen abstraction reactions. Other data: Ea 5 15 kcal mol21 for Br ? reacting with a primary C H bond and Ea 5 13 kcal mol21