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=(BDEofbondsbroken)-(BDEofbondsformed)

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

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.

In the presence of a small amount of bromine, the following light -promoted reaction has been observed.

(a) Write a mechanism for this reaction. Your mechanism should explain how both products are formed. (Hint: Notice which H atom has been lost in both products)

(b) Explain why only this one type of hydrogen atom has been replaced, in preference to any of the other hydrogen atoms in the starting material.

Question: For each reaction, estimate whether S0for the reaction is positive, negative or impossible to predict.

a.

b.The formation of diacetone alcohol:

c.

(a) When n-heptaneburns in a gasoline engine, the combustion process takes place too quickly. The explosive detonation makes a noise called knocking. When 2,2,4 trimethylpentane (isooctane) is burned, combustion takes place in a slower, more controlled manner. Combustion is a free-radical chain reaction, and its rate depends on the reactivity of the free-radical intermediates. Explain why isooctane has less tendency to knock than doesn-heptane

(b) Alkoxy radicals (R-O)are generally more stable than alkyl (R) radicals. Write an equation showing an alkyl free radical (from burning gasoline) abstracting a hydrogen atom from tert-butyl alcohol,(CH3)3COH. Explain whytert-butyl alcohol works as an antiknock additive for gasoline.

(c) Use the information in Table 4-2 (page 203) to explain why toluene (PhCH3) has a very high-octane rating of 111. Write an equation to show how toluene reacts with an alkyl free radical to give a relatively stable radical.

Question: (a) Use bond-dissociation enthalpies from Table 4-2 (page 203), calculate the heat of reaction for each step in the free-radical bromination of methane.

(b) Calculate the overall heat of reaction.

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