Organic Chemistry, 7th Edition L. G. Wade, Jr.

Chapter 4
The Study of Chemical Reactions

Copyright 2010 Pearson Education, Inc.

Introduction
Overall reaction: reactants products Mechanism: Step-by-step pathway. To learn more about a reaction:
Thermodynamics Kinetics

Chapter 4

Chlorination of Methane

Requires heat or light for initiation. The most effective wavelength is blue, which is absorbed by chlorine gas. Many molecules of product are formed from absorption of only one photon of light (chain reaction).
Chapter 4 3

The Free-Radical Chain Reaction

Initiation generates a radical intermediate. Propagation: The intermediate reacts with a stable molecule to produce another reactive intermediate (and a product molecule). Termination: Side reactions that destroy the reactive intermediate.
Chapter 4 4

Initiation Step: Formation of Chlorine Atom

A chlorine molecule splits homolytically into chlorine atoms (free radicals).

Chapter 4

Propagation Step: Carbon Radical

The chlorine atom collides with a methane molecule and abstracts (removes) an H, forming another free radical and one of the products (HCl).
Chapter 4 6

Propagation Step: Product Formation

The methyl free radical collides with another chlorine molecule, producing the organic product (methyl chloride) and regenerating the chlorine radical.
Chapter 4 7

Overall Reaction

Chapter 4

Termination Steps

A reaction is classified as a termination step when any two free radicals join together producing a nonradical compound. Combination of free radical with contaminant or collision with wall are also termination steps.
Chapter 4 9

More Termination Steps

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Lewis Structures of Free Radicals

Free radicals are unpaired electrons. Halogens have 7 valence electrons so one of them will be unpaired (radical). We refer to the halides as atoms not radicals.
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Equilibrium Constant
Keq = [products] [reactants]
For CH4 + Cl2 CH3Cl + HCl Keq = [CH3Cl][HCl] = 1.1 x 1019 [CH4][Cl2]

Large value indicates reaction goes to completion.

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Free Energy Change

DG = (energy of products) - (energy of reactants) DG is the amount of energy available to do work. Negative values indicate spontaneity.
DGo = -RT(lnKeq) = -2.303 RT(log10Keq) where R = 8.314 J/K-mol and T = temperature in kelvins.

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Factors Determining DG
Free energy change depends on:
Enthalpy
DH= (enthalpy of products) - (enthalpy of reactants)

Entropy
DS = (entropy of products) - (entropy of reactants)

DG = DH - TDS

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Enthalpy
DHo = heat released or absorbed during a chemical reaction at standard conditions. Exothermic (-DH) heat is released. Endothermic (+DH) heat is absorbed. Reactions favor products with lowest enthalpy (strongest bonds).
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Entropy
DSo = change in randomness, disorder, or freedom of movement. Increasing heat, volume, or number of particles increases entropy. Spontaneous reactions maximize disorder and minimize enthalpy. In the equation DGo = DHo - TDSo the entropy value is often small.
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Solved Problem 1
Calculate the value of DG for the chlorination of methane.

Solution
DG = 2.303RT(log Keq) Keq for the chlorination is 1.1 x 1019, and log Keq = 19.04 At 25 C (about 298 Kelvin), the value of RT is RT = (8.314 J/kelvin-mol)(298 kelvins) = 2478 J/mol, or 2.48 kJ/mol Substituting, we have

DG = (2.303)(2.478 kJ/mol)(19.04) = 108.7 kJ/mol (25.9 kcal>mol)

This is a large negative value for DG, showing that this chlorination has a large driving force that pushes it toward completion.
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Bond-Dissociation Enthalpies (BDE)

Bond-dissociation requires energy (+BDE). Bond formation releases energy (-BDE). BDE can be used to estimate DH for a reaction. BDE for homolytic cleavage of bonds in a gaseous molecule.
Homolytic cleavage: When the bond breaks, each atom gets one electron. Heterolytic cleavage: When the bond breaks, the most electronegative atom gets both electrons.

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Homolytic and Heterolytic Cleavages

Chapter 4

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Enthalpy Changes in Chlorination

CH3-H + Cl-Cl
Bonds Broken Cl-Cl CH3-H TOTALS

CH3-Cl + H-Cl
Bonds Formed H-Cl CH3-Cl TOTAL

DH (per Mole)
+242 kJ +435 kJ +677 kJ

DH (per Mole)
-431 kJ -351 kJ -782 kJ

DH = +677 kJ + (-782 kJ) = -105 kJ/mol

Chapter 4 20

Kinetics
Kinetics is the study of reaction rates. Rate of the reaction is a measure of how the concentration of the products increase while the concentration of the products decrease. A rate equation is also called the rate law and it gives the relationship between the concentration of the reactants and the reaction rate observed. Rate law is experimentally determined.
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Rate Law
For the reaction A + B C + D, rate = kr[A]a[B]b
a is the order with respect to A b is the order with respect to B a + b is the overall order

Order is the number of molecules of that reactant which is present in the ratedetermining step of the mechanism.

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Activation Energy
The value of k depends on temperature as given by Arrhenius:

k r Ae

Ea / RT

where A = constant (frequency factor) Ea = activation energy R = gas constant, 8.314 J/kelvin-mole T = absolute temperature

Ea is the minimum kinetic energy needed to react.

Chapter 4 23

Activation Energy (Continued)

At higher temperatures, more molecules have the required energy to react.

Chapter 4 24

Energy Diagram of an Exothermic Reaction

The vertical axis in this graph represents the potential energy. The transition state is the highest point on the graph, and the activation energy is the energy difference between the reactants and the transition state.
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Rate-Limiting Step
Reaction intermediates are stable as long as they dont collide with another molecule or atom, but they are very reactive. Transition states are at energy maximums. Intermediates are at energy minimums. The reaction step with highest Ea will be the slowest, therefore rate-determining for the entire reaction.
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Energy Diagram for the Chlorination of Methane

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Rate, Ea, and Temperature

X + CH4 HX + CH3

X F Cl

Ea(per Mole) Rate at 27 C Rate at 227 C 5 17 140,000 1300 300,000 18,000

Br
I

75
140

9 x 10-8
2 x 10-19
Chapter 4

0.015
2 x 10-9
28

Solved Problem 2
Consider the following reaction: This reaction has an activation energy (Ea) of +17 kJ/mol (+4 kcal/mol) and a DH of +4 kJ/mol (+1 kcal/mol). Draw a reaction-energy diagram for this reaction.

Solution
We draw a diagram that shows the products to be 4 kJ higher in energy than the reactants. The barrier is made to be 17 kJ higher in energy than the reactants.

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Conclusions
With increasing Ea, rate decreases. With increasing temperature, rate increases. Fluorine reacts explosively. Chlorine reacts at a moderate rate. Bromine must be heated to react. Iodine does not react (detectably).
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Primary, Secondary, and Tertiary Hydrogens

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Chlorination Mechanism

Chapter 4

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Bond Dissociation Energies for the Formation of Free Radicals

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Solved Problem 3
Tertiary hydrogen atoms react with Cl about 5.5 times as fast as primary ones. Predict the product ratios for chlorination of isobutane.

Solution
There are nine primary hydrogens and one tertiary hydrogen in isobutane.

(9 primary hydrogens) x (reactivity 1.0) = 9.0 relative amount of reaction (1 tertiary hydrogen) x (reactivity 5.5) = 5.5 relative amount of reaction

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Solved Problem 3 (Continued)

Solution
Even though the primary hydrogens are less reactive, there are so many of them that the primary product is the major product. The product ratio will be 9.0:5.5, or about 1.6:1.

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Stability of Free Radicals

Free radicals are more stable if they are highly substituted.

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Chlorination Energy Diagram

Lower Ea, faster rate, so more stable intermediate is formed faster.

Chapter 4 37

Rate of Substitution in the Bromination of Propane

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Energy Diagram for the Bromination of Propane

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Hammond Postulate
Related species that are similar in energy are also similar in structure. The structure of the transition state resembles the structure of the closest stable species. Endothermic reaction: Transition state is product-like. Exothermic reaction: Transition state is reactant-like.
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Energy Diagrams: Chlorination Versus Bromination

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Endothermic and Exothermic Diagrams

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Radical Inhibitors
Often added to food to retard spoilage by radical chain reactions. Without an inhibitor, each initiation step will cause a chain reaction so that many molecules will react. An inhibitor combines with the free radical to form a stable molecule. Vitamin E and vitamin C are thought to protect living cells from free radicals.
Chapter 4 43

Radical Inhibitors (Continued)

A radical chain reaction is fast and has many exothermic steps that create more reactive radicals. When an inhibitor reacts with the radical, it creates a stable intermediate, and any further reactions will be endothermic and slow.
Chapter 4 44

Carbon Reactive Intermediates

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Carbocation Structure

Carbon has 6 electrons, positively charged. Carbon is sp2 hybridized with vacant p orbital.
Chapter 4 46

Carbocation Stability

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Carbocation Stability (Continued)

Stabilized by alkyl substituents in two ways:
1. Inductive effect: Donation of electron density along the sigma bonds. 2. Hyperconjugation: Overlap of sigma bonding orbitals with empty p orbital.

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Free Radicals

Also electron-deficient. Stabilized by alkyl substituents. Order of stability: 3 > 2 > 1 > methyl
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Stability of Carbon Radicals

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Carbanions
Eight electrons on carbon: 6 bonding plus one lone pair. Carbon has a negative charge. Destabilized by alkyl substituents. Methyl >1 > 2 > 3
Chapter 4 51

Carbenes

Carbon is neutral. Vacant p orbital, so can be electrophilic. Lone pair of electrons, so can be nucleophilic.
Chapter 4 52

Basicity of Carbanions

A carbanion has a negative charge on its carbon atom, making it a more powerful base and a stronger nucleophile than an amine. A carbanion is sufficiently basic to remove a proton from ammonia.
Chapter 4 53

Carbenes as Reaction Intermediates

A strong base can abstract a proton from tribromomethane (CHBr3) to give an inductively stabilized carbanion. This carbanion expels bromide ion to give dibromocarbene. The carbon atom is sp2 hybridized with trigonal geometry. A carbene has both a lone pair of electrons and an empty p orbital, so it can react as a nucleophile or as an electrophile.
Chapter 4 54