Module 6 Learning Objectives

• Understand the core concepts and develop

critical skills necessary for understanding
chemical reactivity.
• Discuss the factors that cause reactions to occur
as well as the factors that speed up reactions.
• Draw and analyze energy diagrams.
• Draw and interpret the individual steps of a
reaction.
 Enthalpy

• Enthalpy: a measure of the exchange of energy between the system and its
surroundings during any process.

• Change in enthalpy (ΔH) for any process is defined as the exchange of kinetic
energy between a system and its surroundings under conditions of constant
pressure

• Breaking a bond requires the system to absorb energy

• Forming a bond releases energy from the system

 Change in Enthalpy (ΔH)

• Bonds can break homolytically or heterolytically

• Bond dissociation energy (BDE) or ΔH for bond breaking corresponds

to homolytic bond cleavage. You can find the BDE in Table 6.1 of
Klein
 Change in Enthalpy (ΔH): Energy Diagrams
• Energy diagrams for exothermic vs. endothermic reactions

• Products lower in energy • Products higher in energy

• Energy is released as heat (PE • Energy is consumed (K E converted
converted to KE) to P E)
• ΔH ° is negative • ΔH ° is positive
• Temperature of surroundings • Temperature of surroundings
increases decreases
 Question: How to Read Energy Diagrams

Identify the reactants and products on the following energy diagram

 Bond Dissociation Energy: Exothermic and Endothermic
• Most reactions involve multiple bonds breaking and forming.
• Exothermic reaction – The energy gained by bonds formed exceeds the energy
needed for bonds broken
Products more stable than reactants
• Endothermic reaction – Energy needed for bonds broken exceeds the stability
gained by the bonds formed
Products less stable than reactants
 Question: Calculating Change in Enthalpy
• Use BDE to determine if the reaction below is exothermic (+ΔH) or endothermic (−ΔH)

• ΔH = BDE (bonds broken) − BDE(bonds formed)

Bonds broken = C―H (397 kJ/mol) and Br―Br (193 kJ/mol)
Bonds formed = C―Br (285 kJ/mol) and H―Br (368 kJ/mol)

o ΔH = (397 + 193) − (285 + 368) = − 63 kJ/mol

• ΔH is negative, so the reaction is exothermic
Question: Calculating Change in Enthalpy
 Entropy (ΔS)
• Entropy describes molecular disorderliness, randomness, or freedom.
• Entropy is the number of vibrational, rotational, and translational states the
energy of a compound is distributed.

• The total entropy change (ΔStot) will determine whether a process is

spontaneous.
ΔStot = ΔSsys + ΔSsurr
• For chemical reactions, we must consider the entropy change for both the
system (the reaction) and the surroundings (the solvent usually).
• If ΔStot is positive, the process is spontaneous.
 Entropy Change of the System (ΔS)
• ΔSsys is affected most significantly by two factors, and will be positive…

1. When there are more moles of product than reactant

2. When a cyclic compound becomes acyclic

 Question: Predicting Change in Entropy
For each of the following processes predict the sign of ΔS for the reaction. In other words, will ΔSsys
be positive (an increase in entropy) or negative (a decrease in entropy)?
 Change in Gibbs Free Energy (ΔG): Exergonic
• If a process has a negative ΔG, the process is spontaneous, and the process is
exergonic
• Notice that in this energy diagram, the free energy (G) is plotted rather than
enthalpy (H)
 Change in Gibbs Free Energy (ΔG): Endergonic
• If a process has a positive ΔG, the process is nonspontaneous, and the process is
endergonic.
• An endergonic reaction favors the reactants.
 Equilibria: Relation to ΔG
• Consider an exergonic process with a (−) ΔG, which means the products are favored to form
(spontaneous).
o An equilibrium will eventually be reached.
o A spontaneous process means there will be more products than reactants.
o The greater the magnitude of a (−) ΔG, the greater the equilibrium concentration of
products.
 Question: Reading Energy Diagram
Identify II and III and determine whether the reaction is endergonic or
exergonic as drawn.

a. II is the difference in free energy, III is the

energy of activation, endergonic
b. II is the difference in free energy, III is the
energy of activation, exergonic
c. II is the energy of activation, III is the
difference in free energy, endergonic
d. II is the energy of activation, III is the
difference in free energy, exergonic
 Question
Which of the following would you expect to have the most negative
∆S?
 Question
Based on the following energy diagrams, which reaction is exothermic?
Explanation of Thermodynamic Quantities
 Kinetics: Relationship to ΔG

• Recall that a (−) sign for ΔG tells us a process is thermodynamically favored

(spontaneous).
• That does not tell us anything about the rate or kinetics for the process.
o In other words, ΔG says nothing about how fast a reaction will occur.
• Some spontaneous processes are fast, such as explosions.
• Some spontaneous processes are slow such as C (diamond) → C (graphite)…
this takes millions of years, even though a spontaneous reaction.
 Rate Equations: Rate Law and Reaction Order
• Rate is determined using a rate law:

• The rate depends on a rate constant, and the concentration of

the reactant(s)
• The degree to which a change in [reactant] will affect the rate is
known as the order.
 Kinetics: First, Second, and Third Order Reactions

• The order of a reaction is represented by x and y as follows

Rate = k[A]x[B]y

If [A] is
If [A] is doubled If [A] is doubled
doubled rate is rate is
rate is doubled
doubled
If [B] is doubled quadrupled
If [B] is doubled
….. If [B] is doubled
…… …….
 Factors that affect Kinetics
• The reaction rate is a function of the number of molecular collisions that
will occur in a given period, which is affected by the following factors:
1. The concentrations of the reactants
2. The activation energy
3. The temperature
4. Geometry and sterics
5. The presence of a catalyst
 Factors Affecting the Rate Constant: Activation Energy
• Transition state: Highest energy point in a reaction step
• Activation energy, ΔG‡: Energy required to go from reactant to transition state
 Factors Affecting the Rate Constant: Activation Energy,
Relation to Rate
Activation Energy (Ea) – The energy barrier between reactants and
products
• The lower the activation energy, the faster the rate
Identify (a) the faster reaction, (b) slowest reaction, (c) the exergonic reactions,
and (d) endergonic reactions.
 Factors Affecting the Rate Constant: Temperature
Temperature (T) – Raising temperature will result in a faster rxn.

• At higher T, molecules
have more kinetic
energy.
• At higher T, more
molecules will have
enough energy to
produce a reaction
 Factors Affecting the Rate Constant: Sterics

Steric Considerations – Steric hindrance, and the geometry of a

compound, affects the rate of reaction
• When molecules collide, they must have the correct orientation for
bonds to be made/broken.
• If the reactive conformation of a compound is high energy, it will spend
less time in that conformation, and so the probability of collision
resulting in a reaction is low.
 Catalysts and Enzymes
Catalyst – speeds up the rate of a reaction without being consumed

• Enzymes are catalysts

• Catalyst provides an
alternate, and faster
pathway of reaction
• Catalysts lower the
activation energy
 Reading Energy Diagrams
• Recall that kinetics and thermodynamics are completely different concepts
 Kinetics vs. Thermodynamics
• Consider this energy diagram
which describes two possible
reaction pathways of A + B
• The formation of products C + D
has a lower Ea, and are lower in
energy than E + F.
• So, products C + D form faster
than E + F, and C + D are more
stable than E + F.
• The formation of C + D are
kinetically and
thermodynamically favored.
 Kinetics vs. Thermodynamics

• Now interpret the formation of E + F

versus C + D according to the
following energy diagram
• The formation of products E + F has a
lower Ea and will form faster.
• The products C + D are lower in
energy, thus more stable than E + F.
• The formation of E + F is kinetically
favored, but the formation of C + D
is thermodynamically favored.
 Describing a Reaction Intermediates
• If a reaction occurs in more than one
step, it must involve species that are
neither the reactant nor the final
product
– Called reaction intermediate
• Each step has its own free energy of
activation
Transition States vs. Intermediates
 Nucleophiles & Electrophiles
• Polar reactions – involve ions as reactants, intermediates, and/or products
o Negative charges attracted to positive charges
o Electron-rich species attracted to electron-deficient species

The carbon The carbon

is is
electrophilic nucleophilic
 Polar Reactions
• Nucleophile: Electron-rich species that donate electron pairs to
electrophile in a polar bond-forming reaction
– Is a Lewis base
• Electrophile: Substances that accept electron pairs from a
nucleophile
– Is a Lewis acid
 Examples of Nucleophiles
• Nucleophile – electron-rich species, can donate a pair of electrons
o Nucleophiles are Lewis bases
o More polarizable nucleophile = stronger nucleophile
 Examples of Electrophiles
• Electrophile – electron-deficient species, can accept a pair of
electrons
o Electrophiles are Lewis acids
o Carbocations and partially-positive atoms are electrophilic
 Identifying Nucleophiles and Electrophiles
Identify all nucleophilic and electrophilic centers in the following compound.
 Summary of Nucleophiles & Electrophiles
• Label all the nucleophilic
and electrophilic sites on
the following molecule
 Mechanisms and Arrow Pushing
• Curved arrows are used to show how electrons move as bonds are breaking
and/or forming
o Recall their use in acid-base reactions

• There are four main ways that electrons move in polar

reactions
1. Nucleophilic Attack
2. Loss of a Leaving Group
3. Proton Transfers (Acid/Base)
4. Rearrangements
 Nucleophilic Attack
1. Nucleophilic attack - nucleophile attacking an electrophile

• The tail of the arrow starts at the electron-rich center

• The head of the arrow ends at electron-poor center
• The electrons end up being sharing rather than transferred
 Loss of a Leaving Group
2. Loss of a leaving group – heterolytic bond cleavage, an atom or group takes
the electron pair.

It is common for more than one

curved arrow be necessary to show
the loss of a leaving group:
 Proton Transfers
3. Proton transfer - recall (from chapter 3) that proton transfer requires two
curved arrows
 Rearrangements
4. Rearrangements - carbocations can be stabilized by neighboring groups
through slight orbital overlapping called hyperconjugation
 Rearrangements
4. Rearrangements - Two types of carbocation rearrangement are common

o 1,2-hydride shift

o 1,2-methide shift

• Shifts can only occur from an adjacent carbon.

• Shifts only occur if a more stable carbocation results
Rearrangements: More Examples

More stable,
tertiary carbocation
can form

Tertiary carbocations
typically will rearrange if
a resonance stabilized
cation is formed.