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Introduction to chemical
reactions

C 2004 Barry Linkletter, UPEI

Kinds of Organic Reactions

• In general, we look at what occurs and try to learn how it

happens
• Common patterns describe the changes
– Addition reactions – two molecules combine
– Elimination reactions – one molecule splits into two
– Substitution – parts from two molecules exchange
– Rearrangement reactions – a molecule undergoes changes in
the way its atoms are connected

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How Organic Reactions Occur: Mechanisms

• In a clock the hands (needles) move but the mechanism behind the
face is what causes the movement
• In an organic reaction, we see the transformation that has
occurred. The mechanism describes the steps behind the changes
that we can observe
• Reactions occur in defined steps that lead from reactant to product

C 2004 Barry Linkletter, UPEI

Steps in Mechanisms

• A step involves either the formation or breaking of a covalent bond

• Steps can occur in individually or in combination with other steps
• When several steps occur at the same time they are said to be
concerted

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Types of Steps in Reaction Mechanisms

• Formation of a covalent bond

– Homogenic or heterogenic
• Breaking of a covalent bond
– Homogenic or heterogenic
• Oxidation of a functional group
• Reduction of a functional group

C 2004 Barry Linkletter, UPEI

Homogenic Formation of a Bond

• One electron comes from each fragment

• No electronic charges are involved
• Not common in organic chemistry

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Heterogenic Formation of a Bond

• One fragment supplies two electrons

• One fragment supplies no electrons
• Combination can involve electronic charges
• Common in organic chemistry

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Homolytic Breaking of Covalent Bonds

• Each product gets one electron from the bond

• Not common in organic chemistry

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Heterolytic Breaking of Covalent Bonds

• Both electrons from the bond that is broken

become associated with one resulting fragment
• A common pattern in reaction mechanisms

C 2004 Barry Linkletter, UPEI

Indicating Steps in Mechanisms

• Curved arrows indicate breaking and forming of bonds

• Arrowheads with a “half” head (“fish-hook”) indicate
homolytic and homogenic steps (called ‘radical processes’)
• Arrowheads with a complete head indicate heterolytic and
heterogenic steps (called ‘polar processes’)

Radical processes Polar processes

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Radicals & Reactions involve radicals

• Alkyl groups are abbreviate “R” for radical
– Example: Methyl iodide = CH3I, Ethyl iodide = CH3CH2I, Alkyl
iodides (in general) = RI
• A “free radical” is an “R” group on its own:
– CH3 is a “free radical” or simply “radical” has a single unpaired
electron, shown as: CH3
– Its valence shell is one electron short of being complete

• Radicals react to complete electron octet of valence shell

– A radical can break a bond in another molecule and
abstract a partner with an electron, giving substitution in the
original molecule
– A radical can add to an alkene to give a new radical,
causing an addition reaction

C 2004 Barry Linkletter, UPEI

Steps in Radical Substitution

• Three types of steps

– Initiation – homolytic formation of two reactive species
with unpaired electrons
• Example – formation of Cl atoms form Cl2 and light
– Propagation – reaction with molecule to generate radical
• Example - reaction of chlorine atom with methane to
give HCl and CH3.
– Termination – combination of two radicals to form a
stable product: CH3. + CH3.  CH3CH3

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Polar Reactions and How They Occur

• Molecules can contain local unsymmetrical electron

distributions due to differences in electronegativities
• This causes a partial negative charge on an atom and
a compensating partial positive charge on an
adjacent atom
• The more electronegative atom has the greater
electron density

C 2004 Barry Linkletter, UPEI

Electronegativity of Some Common

Elements
• The relative electronegativity is indicated
• Higher numbers indicate greater electronegativity
• Carbon bonded to a more electronegative element has a partial
positive charge (+)

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Polarizability

• Polarization is a change in electron distribution as a response

to change in electronic nature of the surroundings
• Polarizability is the tendency to undergo polarization
• Polar reactions occur between regions of high electron
density and regions of low electron density

C 2004 Barry Linkletter, UPEI

Generalized Polar Reactions

• An electrophile, (an electron-poor species) combines with a

nucleophile, (an electron-rich species)
• An electrophile is a Lewis acid
• A nucleophile is a Lewis base
• The combination is indicate with a curved arrow from
nucleophile to electrophile

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Example of Polar Reaction: Addition of HBr to

Ethylene

• HBr adds to the  part of C-C double bond

• The  bond is electron-rich, allowing it to function as a nucleophile
• H-Br is electron deficient at the H since Br is much more
electronegative, making HBr an electrophile
HBrd+

C 2004 Barry Linkletter, UPEI

Mechanism of Addition of HBr to Ethylene

• HBr electrophile is attacked by  electrons of ethylene (nucleophile)

to form a carbocation intermediate and bromide ion
• Bromide adds to the positive center of the carbocation, which is an
electrophile, forming a C-Br  bond
• The result is that ethylene and HBr combine to form bromoethane
• All polar reactions occur by combination of an electron-rich site of
a nucleophile and an electron-deficient site of an electrophile

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Using Curved Arrows in Polar Reaction

Mechanisms
• Curved arrows are a way to keep track of changes in bonding in
polar reaction
• The arrows track “electron movement”
• Electrons always move in pairs
• Charges change during the reaction
• One curved arrow corresponds to one step in a reaction
mechanism

C 2004 Barry Linkletter, UPEI

Rules for Using Curved Arrows

• The arrow goes from the nucleophilic reaction site to the

electrophilic reaction site
• The nucleophilic site can be neutral or negatively charged
• The electrophilic site can be neutral or positively charged

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Describing a Reaction: Equilibria, Rates, and

Energy Changes

• Reactions can go either forward or backward to reach

equilibrium
– The multiplied concentrations of the products divided by the
multiplied concentrations of the reactant is the equilibrium
constant, Keq
– Each concentration is raised to the power of its coefficient in
the balanced equation.

aA + bBcC + dD

Keq = [Products]/[Reactants] = [C]c [D]d / [A]a[B]b

C 2004 Barry Linkletter, UPEI

Magnitudes of Equilibrium Constants

• If the value of Keq is greater than 1, this indicates that at

equilibrium most of the material is present as products
– If Keq is 10, then the concentration of the product is ten times
that of the reactant
• A value of Keq less than one indicates that at equilibrium most
of the material is present as the reactant
– If Keq is 0.10, then the concentration of the reactant is ten times
that of the product

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Free Energy and Equilibrium

• The ratio of products to reactants is controlled by their relative
Gibbs free energy
• This energy is released on the favored side of an equilibrium
reaction
• The change in Gibbs free energy between products and reacts is
written as “DG”
• If Keq > 1, energy is released to the surrounding (exergonic
reaction)
• If Keq < 1, energy is absorbed from the surroundings (endergonic
reaction)

C 2004 Barry Linkletter, UPEI

Numeric Relationship of Keq and Free Energy

Change

• The standard free energy change at 1 atm pressure

and 298 K is DGº

• The relationship between free energy change and an

equilibrium constant is:
– DGº = - RT ln Keq where
– R = 1.987 cal/(K x mol)
– T = temperature in Kelvin
– ln = natural logarithm of Keq
– (See the example in the book for a calculation)

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Changes in Energy at Equilibrium

• Free energy changes (DGº) can be divided into
– a temperature-independent part called entropy
(DSº) that measures the change in the amount of
disorder in the system
– a temperature-dependent part called enthalpy (DHº)
that is associated with heat given off (exothermic)
or absorbed (endothermic)
• Overall relationship: DGº = DHº - TDSº

C 2004 Barry Linkletter, UPEI

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).

C 2004 Barry Linkletter, UPEI

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 D G° for the chlorination of methane.

Solution
D 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/kelvin-mol)(298 kelvins) = 2478 J/mol, or 2.48 kJ/mol

Substituting, we have
D G° = (–2.303)(2.478 kJ/mol)(19.04) = –108.7 kJ/mol (–25.9 kcal>mol)
This is a large negative value for D G°, showing that this chlorination has a large driving
force that pushes it toward completion.

C 2004 Barry Linkletter, UPEI

Describing a Reaction: Bond

Dissociation Energies
• Bond dissociation energy (D): Heat change that occurs when a
bond is broken by homolysis

• The energy is mostly determined by the type of bond, independent

of the molecule

– The C-H bond in methane requires a net heat input of 105

kcal/mol to be broken at 25 ºC.

• Changes in bonds can be used to calculate net changes in heat

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Calculation of an Energy Change from Bond

Dissociation Energies

• Addition of Cl-Cl to CH4 (Table 5.3)

• Breaking: C-H D = 438 kJ/mol
Cl-Cl D = 243 kJ/mol
• Making: C-Cl D = 351 kJ/mol
H-Cl D = 432 kJ/mol
Energy of bonds broken = 438 + 243 = 681 kJ/mol
Energy of bonds formed = 351 + 432 = 783 kJ/mol

DHº = 681 – 783 kJ/mol = -102 kJ/mol

C 2004 Barry Linkletter, UPEI

Describing a Reaction: Energy Diagrams and

Transition States (TS)

• The highest energy point

in a reaction step is called
the transition state

• The energy needed to go

from reactant to
transition state is the
activation energy (DG‡)

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First Step in Addition

• In the addition of HBr the

(conceptual) transition-state
structure for the first step
• The  bond between carbons
begins to break
– The C–H bond begins to
form
– The H–Br bond begins to
break

C 2004 Barry Linkletter, UPEI

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
• These are called reaction intermediates or simply
“intermediates”
• Each step has its own free energy of activation
• The complete diagram for the reaction shows the free energy
changes associated with an intermediate

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Formation of a Carbocation Intermediate

• HBr, a Lewis acid, adds to the  bond

• This produces an intermediate with a
positive charge on carbon - a carbocation
• This is ready to react with bromide

C 2004 Barry Linkletter, UPEI

Carbocation Intermediate Reactions with

Anion
• Bromide ion adds an electron pair to the
carbocation
• An alkyl halide produced
• The carbocation is a reactive intermediate

Chemistry 243 - Lecture 6 36

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Reaction Diagram for HBr Addition to Ethylene

• Two separate steps, each with a

own transition state
• Energy minimum between the
steps belongs to the carbocation
reaction intermediate.

C 2004 Barry Linkletter, UPEI

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 reactants 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 rate-determining step of the
mechanism.

C 2004 Barry Linkletter, UPEI

Activation Energy
• The value of k depends on temperature as
given by Arrhenius:
- Ea / RT
k r = Ae

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

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Activation Energy (Continued)

• At higher temperatures, more molecules have

the required energy to react.

Chapter 4

Energy Diagram of an Exothermic

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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

don’t 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.

C 2004 Barry Linkletter, UPEI

Energy Diagram for the Chlorination of

Methane

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Rate, Ea, and Temperature

X + CH4 HX + CH3

X Ea(per Mole) Rate at 27 Rate at 227

°C °C
F 5 140,000 300,000
Cl 17 1300 18,000
Br 75 9 x 10-8 0.015
I 140 2 x 10-19 2 x 10-9

C 2004 Barry Linkletter, UPEI

Solved Problem 2
Consider the following reaction:

This reaction has an activation energy (Ea) of +17 kJ/mol (+4 kcal/mol) and a
D H° 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

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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

C 2004 Barry Linkletter, UPEI

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.

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Rate of Substitution in Bromination of

Propane

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Energy Diagram for 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.

C 2004 Barry Linkletter, UPEI

Energy Diagrams: Chlorination Versus

Bromination

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Endothermic and Exothermic Diagrams

C 2004 Barry Linkletter, UPEI

Biological Reactions

• Reactions in living organisms follow reaction diagrams

too
• They take place in very controlled conditions
• They are promoted by catalysts that lower the
activation barrier
• The catalysts are usually proteins, called enzymes
• Enzymes provide an alternative mechanism that is
compatible with the conditions of life

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