3

Reaction of Alkanes
1. Alkanes are not very reactive, but that they do undergo several types of transformations. These
processes, of which combustion is one example, do not involve acid/base chemistry. Instead, they are called radical reactions.

2. Radical reactions play significant roles in

1. Biochemistry, such as aging and disease processes 2. Environment, such as destruction of the Earths ozone layer 3. Industry, such as manufacture of synthetic fabrics and plastics

3. Radical reactions begin with the breaking of a bond, or bond dissociation. 4. Halogenation, a radical reaction in which a hydrogen atom in an alkane is replaced by
halogen. Turning the alkane into a Haloalkane is suitable for further chemical change.

5. Mechanisms enable us to understand how and why reactions occur, and what products are
likely to form in them.

6. Homolytic Cleavage or Bond Hemolysis, The bond breaks in such a way that the two
bonding electrons divide equally between the two participating atoms or fragments.

7. Because of the unpaired electron, radicals and free atoms are very reactive and usually cannot
be isolated.

8. Radicals and free atoms are present in low concentration as unobserved intermediates in many
reactions, such as the production of polymers and the oxidation of fats that leads to the spoilage of perishable foods.

9. Homolytic cleavage may be observed in nonpolar solvents or even in the gas phase. In
contrast, heterolytic cleavage normally occurs in polar solvents, which are capable of stabilizing ions.

10. Heterolytic cleavage is also restricted to situations where the electronegative of atoms A and B
and the groups attached to them stabilize positive and negative charges, respectively.

Chapter 3, Reaction of Alkanes | Vollhardt Organic Chemistry Structure Function 6th

11. The strength of the bonds between hydrogen and the halogens decreases in the order Fluorine
to Iodine, because the p orbital of the halogen contributing to the bonding becomes larger and more diffuse along the series. Thus, the efficiency of its overlap with the relatively small 1s orbital on hydrogen diminishes.

12. Bond energies generally decrease with the progression from methane to primary, secondary,
and tertiary carbon.

13. Radical stability increases along the series from primary to secondary to tertiary; consequently,
the energy required creating them decreases.

14. Bond-Dissociation Energy (

), Bond homolysis in alkanes yields radicals and free atoms.

The heat required to do so is called the bond-dissociation energy.

15. Alkyl radicals, adopts a nearly planar configuration, best described by

hybridization. The

unpaired electron occupies the remaining p orbital perpendicular to the molecular plane.

16. Hyper-Conjugation. The interaction between a filled orbital and a singly occupied or
unoccupied orbital has a net stabilizing effect.

17. Both Hyper-Conjugation and resonance are forms of electron delocalization. They are
distinguished by type of orbital: 1. Resonance normally refers to type overlap of p orbitals. bonds. (Radicals are

2. Hyper-Conjugation incorporates overlap with the orbitals of stabilized by Hyper-Conjugation)

18. Pyrolysis, when alkanes are heated to a high temperature, both C H bonds and C C bonds
rupture. This process called pyrolysis.

19. In the absence of oxygen, the resulting radicals can combine to form new higher- or lowermolecular-weight alkanes.

20. Hydrogen abstraction, radicals can remove hydrogen atoms from the carbon atom adjacent to
another radical center to give alkenes. This process called hydrogen abstraction.

21. Catalyst, it speeds up the pyrolysis, so that the process occurs at a lower temperature than
otherwise would be the case. The catalyst also causes: 1. Certain products to form preferentially. 2. Reactions are Accelerated 3. Enable new pathways with lower activation energy through which reactants and products are interconverted.

Chapter 3, Reaction of Alkanes | Vollhardt Organic Chemistry Structure Function 6th

4. Change the rate at which equilibrium is established 5. No effect the position of the equilibrium. 6. No effect the overall thermodynamics of a reaction. 7. Many transformations to take place at lower temperatures and under much milder reaction conditions.

22. Cracking, breaking an alkane down into smaller fragments. 23. Chlorination of Alkane, when Methane and Chlorine gas are mixed in the dark at room
temperature, no reaction occurs. The mixture must be heated to a temperature above 300 irradiated with ultraviolet light (denoted by atoms of chlorine. or ) before a reaction takes place. Under such

conditions, methane by itself is completely stable, but Chlorine gas undergoes homolysis to two

24. The mechanism for the chlorination of alkane, in common with the mechanisms of most radical
reactions, consists of three stages: 1. Initiation 2. Propagation 3. Termination

25. Initiation, homolytic cleavage of the Cl Cl bond named as the initiation step because this
bond is the weakest bond among the other bonds. In this step, reactive species are generated. Only a relatively small number of initiation events are necessary to start and continue toward finishing the reaction.

26. The chain is terminated by various combinations of radicals and free atoms.
Small amounts of ethane are identified among the products.

27. The chlorine atoms induce and maintain a radical chain sequence consisting of two
Propagation steps: 1. Hydrogen abstraction to generate the Alkyl radical and HCl 2. Conversion of Alkyl radical by Chlorine gas into Methyl Chloride and regenerated Chlorine gas

28. Fluorine and Bromine, but not Iodine, also react with alkane by similar radical mechanisms. 29. For Fluorine, this step is exothermic. For Chlorine, the same step is slightly endothermic; for
Bromine, it is substantially so, and for Iodine even more so.

Chapter 3, Reaction of Alkanes | Vollhardt Organic Chemistry Structure Function 6th

30. The strong hydrogen fluorine bond is the cause of the high reactivity of Fluorine atoms in
hydrogen abstraction reactions.

31. Even though it is more expensive, Bromine is the reagent of choice for selective radical
halogenations. Chlorinations furnish product mixtures, a problem that can be minimized by 1. Choosing alkanes with only one type of hydrogen 2. Using of a large excess of Alkane in the reaction.

32. Hammond postulate and Potential-energy diagrams, the reaction of a fluorine atom with
methane, is an exothermic process with an early transition state; and the reaction of iodine atom with methane, is an endothermic transformation with a late transition state.

33. Hammond Postulate, the postulate states that the structure of a transition state resembles that
of the species nearest to it in free energy. 1. The transition state of an endothermic reaction resembles the products 2. The transition state of an exothermic reaction resembles the reactants. 3. The transition state that resembles the reactants more than the products is said to be early. 4. The transition state that resembles the products more than the reactants is said to be late.

34. Hammond's postulate is useful for understanding the relationship between the rate of a reaction
and the stability of the products.

35. If two states, for example, a transition state and an unstable intermediate, occur consecutively
during a reaction process and have nearly the same energy content, their inter conversion will involve only a small reorganization of the molecular structures.

36. Iodine does not react with methane to furnish methyl iodide and hydrogen iodide: The first step
costs so much energy that the second step, although exothermic, cannot drive the reaction.

37. Although secondary C H bonds generally undergo dissociation faster than do their primary
counterparts, their relative reactivity very much depends on the nature of the attacking species, the strength of the resulting H X bond, and the temperature.

38. A comparison of the heats of combustion of isomeric alkanes reveals that their values are
usually not the same.

39. The heats of combustion values of alkanes and other organic molecules give quantitative
estimates of their energy content and, therefore, their relative stabilities.

Chapter 3, Reaction of Alkanes | Vollhardt Organic Chemistry Structure Function 6th