Chapter 5: Overview of Chemical Reactions

Coverage: 1. Types of Organic Reactions 2. Mechanisms and Curved Arrows 3. Radical and Polar Reactions 4. Reactive Intermediates and Transition States 5. Thermodynmics 6. Kinetics
End of Chapter Problems: 5.23-5.32, 5.39, 5.40

Goals: 1. Know the types of organic reactions and be able to recognize when you see them. 2. Know how to used curved arrows when writing mechanisms. 3. Understand the difference between radical and polar reactions. 4. Know the nature of reactive intermediates in organic chemistry. 5. Understand how a transition state differs from a reactive intermediate. 6. Understand what controls the equilibrium position of a reaction (thermodynamics). 7. Understand what controls the rate of a reaction (kinetics).

Mechanism step-by-step description of bond-breaking and bond-making processes to give product. Bond-breaking Bond-making

Curved arrows are used to indicate flow of electrons in these processes.

Curved Arrows
1. Electrons move from a nucleophile to a electrophile

+ N: + E-X N-E+ + X

.. HO:..
Nucleophile

.. CH3-I: ..
Electrophile

.. HO-CH3 ..

.. :I:..

The above reacton is an example of a substitution reaction. The OH substitutes for the I atom in the reaction.

2. The nucleophile can either be negatively charged or neutral. However, it must possess a nonbonded pair of electrons.

N: N:

+ +

E E

N-E N-E

Neutral product

Negative product

3. The electrophile can either be positively charged or neutral.

N:

E+

N-E+

Positive Product

N:

E+

N-E

Neutral Product

Important: Remember that charge must be conserved in going from left to right in the reaction.

Kinds of Organic Reactions

1. Addition reactions - two reactants are added together to form a single new product.

N:
H C C H H

+
H

N-E
H Br

H-Br

H C C H H H

2. Elimination Reactions - the reverse of Addition, a molecule splits into two products
H Br H C C H H H H C C H H

H-Br

3. Substitution Reactions two reactants exchange parts to give a two new products

CH4

Cl

Cl

light

CH3Cl

H Cl

4. Rearrangement Reactions - a molecule undergoes a reorganization of bonds to yield an isomeric product.

C7H16

C7H16

Reactive Intermediates
1. Free Radicals Neutral intermediates possessing unpaired electrons CH3. CH3CH2.

Carbon is sp2 hybridized.

.
H C

H H

Radical is electron deficient and therefore acts as an electrophile. Stabilized by the presence of alkyl group.

Stabilized by the presence of alkyl groups.

R R R C H R H C H H H C H

R C R

3o Most Stable

2o

1o

methyl Least Stable

Radical Reactions
Chlorination of Methane Overall Reaction: CH4 + Cl2 CH3Cl + HCl Initiation light or heat is required to produce the initial radicals.
Cl2 2 Cl.

Propagation these two steps repeat until one or more reactant is consumed.
Cl. + CH4 HCl + CH3. CH3 . + Cl2 CH3Cl + Cl

Termination this step causes the reaction to stop.

CH3. + CH3. + CH3. CH3CH3 Cl. CH3Cl

2. Carbenium (Carbocation) Intermediates Carbenium are positively charged and electron-deficient. Strong Lewis acids and electrophiles CH3+ CH3CH2+ + empty p orbital

Central Carbon is sp2 hybridized

H C

H H

Stabilized by the presence of alkyl groups due to hyperconjugative effect or donation of sigma electrons of C-H bond to empty p orbital.

 Order of Stability same as Radical Stability

R R C R
+

R R C H
+

R H C H
+

H H C H
+

3o Most Stable

2o

1o

methyl Least Stable

Polar Reaction involving Carbenium ion intermediate: Addition of HBr to ethylene.

H C C H H H H Br

H-Br

H C C H H H

Electrophile

Nucleophile

Why is the double bond so reactive? Answer: The Pi electrons are more loosely held.

3. Carbanion Intermediates Carbanions are negatively charged and electron-rich. CH3

CH3CH2

Central Carbon is sp3 hybridized

-:
sp3 orbital Destabilized by the presence of alkyl groups.
R R C R R R C H R H C H

H H H

H H C H

3o Least Stable

2o

1o

methyl Most Stable

4. Carbenes Intermediates Uncharged reactive intermediates containing a divalent carbon atom. Simplest carbene has the formula :CH2, called methylene Central Carbon is sp2 hybridized Empty p orbital

Br Br C

Nonbonding electrons paired in this sp2 orbital

Dibromocarbene

The carbene can act either as an electrophile or a nucleophile. Why? Answer: It has an empty p orbital electrophile It has a nonbonding pair of electrons - nucleophile

Thermodynamics
Thermodynamics is the branch of chemistry that deals with energy changes that accompanies chemical and physical reactions. A + B C + D

Keq = [products]/[reactants] = [C][D]/[A]/[B]

Example:

CH4 + Cl2

CH3Cl

HCl

Radical Chlorination

Keq = 1.1 x 1019 i.e. this reaction goes to completion! The standard Gibbs free energy change, Go, can be calculated from Keq.. G = -RT (ln Keq) R = 1.987 cal/K mol T = absolute temperature in Kelvin e = 2.718, the base of the natural logarithms

If Go is negative, then forward reaction is favored at equilibrium (Keq > 1) If Go is positive, then the forward reaction is unfavorable (Keq < 1) What factors contribute to Go? Go = Ho - T So Go = change in free energy Ho = change in enthalpy (heat) So = change in entropy (amount of disorder)

At low temperatures, the TSo term is small compared to Ho, so chemists often make the approximation that Go Ho

Change in Enthalpy, Ho, the amount of heat absorbed or released by the reaction. Measure of the relative strengths of bonds in the products and reactants. If weaker bonds are broken and stronger bonds are formed, heat is released and the reaction is termed exothermic (negative Ho). If stronger bonds are broken and weaker bonds are formed, heat is absorbed and the reaction is termed endothermic (positive Ho). Example: Free radical chlorination of methane Ho = -26.0 kcal/mol exothermic reaction Change in Entropy, So, is the change in the amount of randomness in the reaction. A positive value means that the products have more randomness (degrees of freedom). Value reflects the number of molecules in the reactant versus the product as well as the flexibility of the molecules. Example: Free radical chlorination of methane So +2.9 cal/K mol T So = 298 (+2.9) = -860 cal/mol or 0.860 kcal/mol Very small!!!!

Conclusion: Enthalpy changes dominate in the free radical chlorination of methane!!!

How can we calculate the enthalpy change for a reaction? Answer: Utilize Bond Dissociation Energies (BDE) obtained from Tables in the text.

A B
Homolytic Cleavage only!!

A . + B.

Ho Bond Dissociation Energy

H3C

Cl

Cl

light H3C Cl
Bonds Made
H Cl

H Cl

Bonds Broken
Cl
H3 C

Cl
H

+58 kcal/mol +104 kcal/mol +162 kcal/mol

-103 kcal/mol -84 kcal/mol -187 kcal/mol

H3C Cl

Ho = +162 + (-187) = -25 kcal/mol

Focus on Propagation since it is the major sequence of reactions that produces products of CH3Cl and HCl. a.

Cl

+ +
Ho for

CH4 Cl2

HCl CH3Cl

+ +

CH3 Cl

Ho = +1 kcal/mol Ho = -26 kcal/mol Ho = -25 kcal/mol

b. CH3

Calculate a.

each step: Bonds Made H-Cl -103 Bonds Made H3C-Cl -84

Bonds Broken H3C-H +104 Bonds Broken Cl-Cl +58

b.

What do the transition states for these reactions look like? Use dotted lines to show bonds breaking and making.

Propagation Steps

Rate-determining Step Highest energy step of multistep reaction. It represents the bottle-neck of the reaction.

Ea1 = 4 kcal/mol

Ea2 = 1 kcal/mol

Ho Kcal/mol

-----------------CH . + Cl
3

CH4 + Cl. Hooverall = -25

The first step is rate-determining due to its highest activation energy.

------------------------------

CH3Cl + Cl.

Reaction Coordinate

Kinetics and Energy of Activation

Energy of Activation is the minimum kinetic energy the molecules must possess to overcome the repulsion between their electron clouds when they collide. If they do not have sufficient energy, no reaction will occur.

kr = Ae-Ea/RT
kr rate constant A frequency factor Ea energy of activation R gas constant T absolute temperature The higher the temperature, the faster the reaction (larger kr) The higher the Energy of Activation, the slower the reaction (smaller kr)