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Chemical Reactions of Alkane

Read Chapter 4 in Organic Chemistry, 7th Edition, L. G. Wade, Jr., 2010, Prentice Hall (Pearson Education)
2010, Prentice Hall

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

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).

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.

Initiation Step: Formation of Chlorine Atom

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

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).

Propagation Step: Product Formation

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

Overall Reaction

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.

More Termination Steps

Lewis Structures of Free Radicals

Free radicals are unpaired electrons. Halogens have 7 valence electrons so one of them will be unpaired (radical). We usually refer to the halide radicals as atoms.

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.

Free Energy and Equilibrium Constant

G = (energy of products) - (energy of reactants) G is the amount of energy needed to do work. Negative values indicate spontaneity. Go = -RT(lnKeq) = -2.303 RT(log10Keq) where R = 8.314 J/Kmol and T = temperature in Kelvins.

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

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

G = H - TS

Enthalpy
Ho = heat released or absorbed during a chemical reaction at standard conditions. Exothermic (H is negative) heat is released. Endothermic (H is positive) heat is absorbed. Reactions favor products with lowest enthalpy (strongest bonding).

Entropy
So = 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 Go = Ho - TSo the entropy value is often small.

Problem 1
Calculate the value of G for the chlorination of methane.
Keq = 1.1 x 1019 Solution G = 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/K-mol)(298 K) = 2478 J/mol, or 2.48 kJ/mol Substituting, we have G = (2.303)(2.478 kJ/mol)(19.04) = 108.7 kJ/mol (25.9 kcal/mol) This is a large negative value for G, showing that this chlorination has a large driving force that pushes it toward completion.

Bond-Dissociation Energy (BDE)

Bond-dissociation requires energy (+BDE). Bond formation releases energy (-BDE). BDE can be used to estimate H 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.

Homolytic and Heterolytic Cleavages

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

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

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

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

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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.

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. kr is the rate constant.

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Rate Constant and 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/K-mole T = absolute temperature Ea is the minimum kinetic energy needed to react.

Activation Energy (Ea)

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

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Energy Diagram of an Exothermic Reaction

The transition state is the highest point on the graph, and the activation energy (Ea) is the energy difference between the reactants and the transition state.

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

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Energy Diagram for the Chlorination of Methane

Intermediate

Intermediates & rate-determining step

Intermediates are at energy minimums. Reaction intermediates are stable as long as they dont collide with another molecule or atom. Intermediates are usually much more reactive than their starting reactants and products. The reaction step with highest Ea will be the slowest, therefore rate-determining for the entire reaction.

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Rate, Ea, and Temperature

X + CH4 HX + CH3

X F Cl Br I

Ea(kJ/mole) 5 17 75 140

Rate at 27 C Rate at 227 C (M/s) (M/s) 140,000 300,000 1300 9 x 10-8 2 x 10-19 18,000 0.015 2 x 10-9

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

40%

60%

Chlorination Mechanism

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Bond Dissociation Energies for the Formation of Free Radicals

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

(9 1 hydrogens) x (reactivity 1.0) = 9.0 relative amount (1 3 hydrogen) x (reactivity 5.5) = 5.5 relative amount

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Problem 3 (Continued)
Note 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.

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.

Rate of Substitution in the Bromination of Propane

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Energy Diagram for the Bromination of Propane

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 VS Bromination

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.

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Radical Inhibitors (Continued)

I

Stable Intermediate

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.

Free Radicals

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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