6.

1 Enthalpy
• Enthalpy (ΔH or q) is the heat energy exchange between the
reaction and its surroundings
• Breaking a bond requires the system to absorb energy

The electrons must absorb

Kinetic energy to overcome
the stability of the bond

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 6.1 Enthalpy (ΔH)
• Bonds can break homolytically or heterolytically

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

corresponds to homolytic bond cleavage

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 6.1 Bond Dissociation Energy

• More BDEs can be found in table 6.1

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 6.1 Bond Dissociation Energy
• 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

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 6.1 Enthalpy (ΔH)
• Energy diagrams for exothermic vs. endothermic reactions

• Products lower in energy • Products higher in energy

• Energy is released as heat • Energy is consumed
(PE converted to KE) (KE converted to PE)
• DH˚ is negative • DH˚ is positive
• Temp of surroundings increases • Temp of surroundings consumed

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 6.1 Enthalpy (ΔH)
• The sign (+/-) of ΔH indicates if the reaction is exothermic or
endothermic.

• An energy diagram is often used to describe the kinetics and

thermodynamics of a chemical reaction
– Potential energy (PE) is described by the y-axis
– Reaction progress described by the x-axis (reaction coordinate)

• Practice with SkillBuilder 6.1

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 6.1 Enthalpy (ΔH)
• Practice the Skill 6.1 – Use BDE’s to determine if the following
reaction is exothermic (+DH) or endothermic (-DH)

• DH = 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)
• DH = (397 + 193) – (285 + 368) = -63 kJ/mol

• DH is negative, so the reaction is exothermic

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 6.2 Entropy (ΔS)
• Exothermic and endothermic reactions can occur spontaneously
(most reactions are exothermic though)

• Enthalpy (DH) and entropy (DS) must both be considered when

predicting whether a reaction will occur

• Recall that entropy can be described as molecular disorder,

randomness, or freedom

• Entropy is actually the number of vibrational, rotational, and

translational states the energy of a compound is distributed.

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 6.2 Entropy (ΔS)
• Consider why a gas will expand and spread out into an empty
container

• The number of states the molecules spread across increases with

increasing volume.

• More volume for gas to occupy = greater entropy

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 6.2 Entropy (ΔS)
• The total entropy change (DStot) will determine whether a process
is spontaneous

• 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.

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 6.2 Entropy (ΔS)
• ΔSsys is affected most significantly by two factors, and will be
positive…

1. When there are more moles of product than reactant

1. When a cyclic compound becomes acyclic

Practice with Conceptual Checkpoint 6.3

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 6.3 Gibbs Free Energy (ΔG)
• Recall the spontaneity of a process depends only on ΔStot

• ΔSsurr is actually a function of ΔHsys and temperature (T)

which gives us a new equation for ΔStot

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 6.3 Gibbs Free Energy (ΔG)
• Multiply both sides by temperature (T)

• ΔG is the Gibbs Free Energy. A negative value of DG means the

reaction is spontaneous, and a positive value is a nonspontaneous
reaction.

DH is the change in the

TDS is the change in the
Entropy of the surroundings
entropy of the system

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 6.3 Gibbs Free Energy (ΔG)
• Consider the following reaction, which is spontaneous:

• Since the reaction is spontaneous, DG must be negative

• We also know that TDS will be negative value because entropy is

decreasing (2 molecules become 1).
• So, it must be true that DH is a negative value, in order for DG to
be negative overall.
• In other words, the entropy of the surroundings is increasing
more than the entropy of the system is increasing
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 6.3 Gibbs Free Energy (ΔG)
• If a process has a negative ΔG, the process is spontaneous, and
the process is exergonic

• Notice that in this energy

diagram, is is the free
energy (G) is plotted
rather than enthalpy (H)

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 6.3 Gibbs Free Energy (ΔG)
• If a process has a positive ΔG, the process is nonspontaneous, and
the process is endergonic

• An endergonic reaction
favors the reactants

• Practice with conceptual

checkpoint 6.4

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 6.4 Equilibria
• Consider an exergonic process with a (-) ΔG, which means the
products are favored to form (spontaneous).
– an equilibrium will
eventually be reached

– A spontaneous process
means there will be more
products than reactants

– The greater the

magnitude of a (-)ΔG, the
greater the equilibrium
concentration of
products
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 6.4 Equilibria
• Why doesn’t an exergonic process react 100% to give products?
Why will some reactants still remain at equilibrium?

• As [A] and [B] decrease

collisions between A and
B will occur less often

• As [C] and [D] increase,

collisions between C and
D will occur more often

• Eventually the forward

and reverse reaction
rates will be equal
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 6.4 Equilibria
• An equilibrium constant (Keq) is used to show the degree to which
a reaction is product or reactant favored

• Keq, ΔG, ΔH, and ΔS are thermodynamic terms. The only describe
the relative stability of the products and reactants, but not the
rate at which they are formed

• Practice with checkpoint 6.6

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 6.4 Equilibria
• Notice that increasing (or decreasing) the value of DG by about 6
kJ/mol corresponds to a 10x change in the equilibrium constant

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 6.5 Kinetics
• Recall that a (-) sign for ΔG tells us a process is product favored
(spontaneous)

• That does NOT tell us anything about the RATE or kinetics for the
process.
– In other words, DG 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) à C

(graphite)… this takes millions of years, even though a
spontaneous reaction

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 6.5 Kinetics
• The reaction rate is a function of the number of molecular
collisions that will occur in a given period of time, 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

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 6.5 Rate Equations
• 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.

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

If [A] is doubled If [A] is doubled If [A] is doubled

rate is doubled rate is doubled rate is quadrupled

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 6.5 Factors Affecting the Rate Constant
1. Activation Energy (Ea) – The energy barrier between reactants
and products

Free
energy
(G)

• Ea is the minimum amt. of

energy required for a
molecular collision to result
in a reaction

Copyright © 2017 John Wiley & Sons, Inc. All rights reserved. 6-26 Klein, Organic Chemistry 3e
 6.5 Factors Affecting the Rate Constant
1. Activation Energy (Ea) – The energy barrier between reactants
and products
• As Ea increases, the number of molecules possessing enough
energy to react decreases…

Copyright © 2017 John Wiley & Sons, Inc. All rights reserved. 6-27 Klein, Organic Chemistry 3e
 6.5 Factors Affecting the Rate Constant
1. Activation Energy (Ea) – The energy barrier between reactants
and products
• The lower the activation energy, the faster the rate

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 6.5 Factors Affecting the Rate Constant
2. 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

Copyright © 2017 John Wiley & Sons, Inc. All rights reserved. 6-29 Klein, Organic Chemistry 3e
 6.5 Factors Affecting the Rate Constant
3. Steric Considerations – Steric hindrance, and the geometry of a
compound, affects the rate of reaction

• When molecules collide, they have to 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

• This will be further explored in Chapter 7.

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 6.5 Catalysts and Enzymes
4. 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

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 6.6 Reading Energy Diagrams
• Recall that kinetics and thermodynamics are completely
different concepts

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 6.6 Kinetics vs. Thermodynamics
• Consider the energy diagram below, 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

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 6.6 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

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 6.6 Transition States vs. Intermediates

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 6.6 Transition States vs. Intermediates
• A transition state is the high
energy state a reaction
passes through

• Transition states are fleeting;

they cannot be observed

• On an energy diagram,
transition states are energy
maxima, and represent the
transition as bonds are made
and/or broken

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 6.6 Transition States vs. Intermediates
• An intermediate is an intermediate species formed during the
course of a reaction. They are energy minima on the diagram.
• Intermediates are observable. They are an actual chemical
species that exists for a period of time before reacting further

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 6.6 The Hammond Postulate
• Two points on an energy diagram that are close in energy should
be similar in structure

• Based on this assumption,

we can generalize the
structure of a transition
state, depending on
whether the reaction is
exothermic or endothermic

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 6.6 The Hammond Postulate
• Exothermic rxn – transition states resembles reactant(s)
• Endothermic rxn – transition state resembles product(s)

• Practice with Conceptual Checkpoint 6.7

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 6.7 Nucleophiles & Electrophiles
• Polar reactions – involve ions as reactants, intermediates,
and/or products
– Negative charges attracted to positive charges
– Electron-rich species attracted to electron-deficient species

The carbon is The carbon is

electrophilic nucleophilic

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 6.7 Nucleophiles
• Nucleophile – electron rich species, can donate a pair of electrons
– Nucleophiles are Lewis bases
– More polarizable nucleophile = stronger nucleophile

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 6.7 Electrophiles
• Electrophile – electron deficient species, can accept a pair of
electrons
• Electrophiles are Lewis acids
• Carbocations and partially-positive atoms are electrophilic

• Practice with SkillBuilder 6.2

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 6.7 Nucleophiles & Electrophiles
• Label all of the
nucleophilic and
electrophilic sites on
the following molecule

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 6.8 Mechanisms and Arrow Pushing
• Curved arrows are used to show how electrons move as bonds
are breaking and/or forming
• 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
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 6.8 Nucleophilic Attack
1. Nucleophilic attack - nucleophile attacking an electrophile

• The tail of the arrow starts on the electrons (- charge)

• The head of the arrow ends on a nucleus (+ charge)
• The electrons end up being sharing rather than transferred

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 6.8 Nucleophilic Attack
1. Nucleophilic attack may require more than one curved arrow

• The alcohol (nucleophile) attacks a carbon with a δ+ charge.

• The second arrow could be thought of as a resonance arrow.

Copyright © 2017 John Wiley & Sons, Inc. All rights reserved. 6-46 Klein, Organic Chemistry 3e
 6.8 Nucleophilic Attack
1. Nucleophilic attack - Pi bonds can also act as a nucleophiles

• Note that only one of the carbon atoms from the pi bond uses
the pair of electrons (from the pi bond) to attack the electrophile

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 6.8 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:

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 6.8 Proton Transfers
3. Proton transfer - Recall (from Chapter 3) that proton transfer
requires two curved arrows

• The deprotonation of a compound is sometimes shown with just

a single arrow and “-H+” above the rxn arrow.

or

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 6.8 Proton Transfers
• Multiple arrows may be
necessary to show the
complete electron flow when a
proton is exchanged

• Such electron flow can also be thought of as a proton transfer

combined with resonance

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 6.8 Rearrangements
4. Rearrangements - Carbocations can be stabilized by neighboring
groups through slight orbital overlapping called hyperconjugation

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 6.8 Rearrangements
• Hyperconjugation explains the carbocation stability trend below

• Increasing the substitution increases the stability of a

carbocation, due to the increasing number of adjacent sigma
bonds aligned with the empty p-orbital.

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 6.8 Rearrangements
4. Rearrangements - Two types of carbocation rearrangement are
common

– 1,2-hydride shift

– 1,2-methide shift

• Shifts can only occur from an adjacent carbon.

• Shifts only occur if a more stable carbocation results

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 6.9 Combining Patterns of Arrow Pushing
• Multistep reaction mechanisms are simply a combination of one
or more of the 4 patterns covered thus far:

• Often two of the patterns occur in a single mechanistic step:

Nucleophilic attack and the loss

of a leaving group simultaneously

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 6.10 Drawing Curved Arrows
1. The curved arrow starts on a pair of electrons (a shared pair in a
bond, or a lone pair)

– The second arrow shown below is drawn incorrectly

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 6.10 Drawing Curved Arrows
2. The head of a curved arrow shows either the formation of a bond,
or the formation of a lone pair

3. The head of a curved arrow can never show carbon forming more
than 4 bonds

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 6.10 Drawing Curved Arrows
4. Any curved arrow drawn should describe one of the 4 patterns
discussed thus far.

The arrow below is unreasonable. It violates the octet, and

doesn’t match one of the 4 patterns

• Practice with SkillBuilder 6.5

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 6.11 Carbocation Rearrangements
• When you encounter a carbocation, you must consider if
rearrangement (Hydride and methyl shift) could result in a more
stable carbocation

This is a secondary carbocation. Could it rearrange to a more

stable tertiary carbocation?

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 6.11 Carbocation Rearrangements
• When you encounter a carbocation, you must consider if
rearrangement will occur
1. Identify H atoms and/or methyl groups on neighboring carbon
atoms

2. Determine if the shifting of one of these groups give a more stable

carbocation
more stable, tertiary
carbocation can form

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 6.11 Carbocation Rearrangements
• Tertiary carbocations typically will not rearrange unless a
resonance stabilized cation is formed.

• Here, an allylic carbocation if formed

• Practice with SkillBuilder 6.6

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 6.12 Reversible and Irreversible
Reaction Arrows
• Some reactions are drawn as equilibria, and others are drawn as
irreversible.

• The question of reversibility is both a kinetic and a thermodynamic

question.

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 6.12 Reversible and Irreversible
Reaction Arrows
• If the attacking nucleophile is also a good leaving group, it will be
a reversible attack

• The reverse process occurs at an appreciable rate

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 6.12 Reversible and Irreversible
Reaction Arrows
• If the attacking nucleophile is a poor leaving group, it will
essentially be an irreversible attack

• The reverse reaction does not occur

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 6.12 Reversible and Irreversible
Reaction Arrows
• The loss of a leaving group is virtually always reversible

• Most of the leaving groups encountered can act as nucleophiles

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 6.12 Reversible and Irreversible
Reaction Arrows
• All proton transfers are reversible.
• But, if the pKa difference is 10 units or more, it can be considered
irreversible

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 6.12 Reversible and Irreversible
Reaction Arrows
• Carbocation rearrangements are generally irreversible

• Thermodynamically, there is no driving force for a more stable

carbocation to rearrange to a less stable one.

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 6.12 Reversible and Irreversible
Reaction Arrows
• When considering thermodynamic equilibrium, in addition to
comparing relative energies, Le Châtelier’s principle must also be
considered.

• One of the products (N2) is a gas, and will escape the reaction
mixture. It becomes impossible for the reaction to be reversible

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