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Use the bond-dissociation enthalpies in Table 4-2 (page 203) to calculate the heats of reaction for the two possible first propagation steps in the chlorination of isobutane. Use this information to draw a reaction-energy diagram like Figure 4-8, comparing the activation energies of the two radicals.

Short Answer

Expert verified

-9KJ/mol (Propagation step I)

-29KJ/mol (Propagation step II)

Step by step solution

01

Free radicals

An atom or group of atoms containing odd or unpaired electrons is known as free radical. The unpaired electron is represented by a single unpaired dot in the formula. Free radicals are electrically neutral. They are highly reactive species formed by homolytic fission of a covalent bond.

02

Steps involved in free radical chain reaction

In a free-radical chain reaction, free radicals are generally created in the initiation step. A free radical and a reactant are combined in the propagation step. In the termination step, the product will be formed.

03

Bond dissociation enthalpy (BDE)

BDE is the amount of enthalpy required to break a bond homolytically in such a way that each bonded atom retains one of the bond’s two electrons.

Mathematically,△H0=∑(BDE  of  bonds  broken)-∑(BDE  of  bonds  formed)

04

Activation energy ( Ea )

Activation energy is the extra energy that the molecules of reactants have to absorb so that their energy becomes equal to the threshold energy.

05

Transition state or activated complex

The highest energy state in a molecular collision that leads to reaction is the transition state. During the formation of this complex, old bonds start breaking, and new bonds are formed.

06

Intermediate

Intermediate is a species that exists for a finite amount of time and has some stability, although its lifespan is short.

07

Reaction energy diagrams

A reaction energy diagram is used to understand the concepts of activation energy and transition state graphically. The vertical axis of the diagram represents the total potential energy of all the species present in the reaction. The horizontal axis represents the reaction coordinate that gives the progress of the reaction, proceeding from reactants on the left to products on the right. The highest point on the graph is the transition state, and the activation energy is the difference in energy between the reactants and the transition state.

08

Two possible first propagation steps in the chlorination of isobutane

Therefore, the enthalpy of the reaction for the propagation of step I is -9KJ/mol

Therefore, the enthalpy of the reaction for the propagation of step IIis -29KJ/mol .

09

Reaction-energy diagram for chlorination of isobutane

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Most popular questions from this chapter

Question: (a) Write the propagation steps leading to the formation of dichloromethane (CH2Cl2).

(b) Explain why free-radical halogenation usually gives mixture of products.

(c) How could an industrial plant control the proportions of methane and chlorine to favor production of CCl4? To favor production of CH3Cl?

Acetylacetone (pentane -2, 4-dione)reacts with sodium hydroxide to give water and the sodium salt of a carbanion. Write a complete structural formula for the carbanion, and use resonance forms to show the stabilization of the carbanion.

Question: Each of the following proposed mechanisms for the free-radical chlorination of methane is wrong. Explain how the experimental evidence disproves each mechanism.

(a)

CI2+³ó±¹â†’C±õ2(anactivatedformofCI2)CI2+CH4→H°ä±ô+°ä±á3Cl(b)CH4+hv→CH3+HCH3+Cl2→CH3Cl+ClCl+H→HCl

When exactly 1 mole of methane is mixed with exactly 1 mole of chlorine and light is shone on the mixture, a chlorination reaction occurs. The products are found to contain substantial amounts of di-, tri-, and tetrachloromethane, as well as unreacted methane.

(a) Explain how a mixture is formed from this stoichiometric mixture of reactants, and propose mechanisms for the formation of these compounds from chloromethane.

(b) How would you run this reaction to get a good conversion of methane toCH3Cl? Of methane to CCl4?

The chlorination of pentane gives a mixture of three monochlorinated products.

(a) Draw their structures.

(b) Predict the ratios in which these monochlorination products will be formed, remembering that a chlorine atom abstracts a secondary hydrogen about 4.5 times as fast as it abstracts a primary hydrogen.

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