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Understanding Symbol in Reaction
Understanding Symbol in Reaction
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Understanding Organic Reactions
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Understanding Organic Reactions
Writing Equations for Organic Reactions:
• When two sequential reactions are carried out without
drawing any intermediate compound, the steps are
numbered above or below the reaction arrow. This
convention signifies that the first step occurs before the
second step, and the reagents are added in sequence.
Omitting the numbers means they are present together.
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Kinds of Organic Reactions
Substitution Reactions:
• A substitution is a reaction in which an atom or a group
of atoms is replaced by another atom or group of atoms.
• Below, Y replaces Z on a carbon atom.
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Kinds of Organic Reactions
Substitution Reactions:
• Substitution reactions involve breaking one σ bond and
forming another at the same carbon atom.
• In a nucleophilic attack, the group that departs needs to
have some stability to exist by itself (a weak base).
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Kinds of Organic Reactions
Elimination Reactions:
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Kinds of Organic Reactions
Elimination Reactions:
• In an elimination reaction, two groups X and Y are removed
from a starting material.
• Two σ bonds are broken, and a π bond is formed between
adjacent atoms.
• The most common examples of elimination occur when X = H
and Y is a heteroatom more electronegative than carbon.
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Kinds of Organic Reactions
Addition Reactions:
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Kinds of Organic Reactions
Addition Reactions:
• In an addition reaction, new groups X and Y are added
to the starting material. A π bond is broken and two σ
bonds are formed.
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Kinds of Organic Reactions
Addition and Elimination Reactions:
• Addition and elimination reactions are exactly
opposite. A π bond is formed in elimination reactions,
whereas a π bond is broken in addition reactions.
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Understanding Organic Reactions
Bond Making and Bond Breaking are the essence of
chemical reactions:
• A reaction mechanism is a detailed description of how
bonds are broken and formed as starting material is
converted into product.
• A reaction can occur either in one step or a series of steps.
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Understanding Organic Reactions
Homolytic Bond Breaking:
• Regardless of how many steps there are in a reaction, there
are only two ways to break (cleave) a bond: the electrons in
the bond can be divided equally or unequally between the
two atoms of the bond.
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Understanding Organic Reactions
Heterolytic Bond Breaking:
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Understanding Organic Reactions
Homolysis:
• Homolysis generates two uncharged species with
unpaired electrons.
• A reactive intermediate with a single unpaired electron is
called a radical.
• Radicals are highly unstable because they contain an atom
that does not have an octet of electrons.
Heterolysis:
• Heterolysis generates a carbocation or a carbanion.
• Both carbocations and carbanions are unstable
intermediates. A carbocation contains a carbon surrounded
by only six electrons, and a carbanion has a negative charge
on carbon, which is not a very electronegative atom.
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Understanding Organic Reactions
Radicals, Carbocations and Carbanions
Figure 6.2 Three reactive intermediates resulting
from homolysis and heterolysis of a C – Z bond
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Understanding Organic Reactions
Radicals, Carbocations and Carbanions
• Radicals and carbocations are electrophiles because they
contain an electron deficient carbon (sp2 carbon atoms).
• Carbanions are nucleophiles because they contain a
carbon with a lone pair (sp3 carbon atoms).
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Understanding Organic Reactions
Bond Making:
• Bond formation occurs in two different ways.
• Two radicals can each donate one electron to form a
two-electron bond.
• Alternatively, two ions with unlike charges can come
together, with the negatively charged ion donating both
electrons to form the resulting two-electron bond.
• Bond formation always releases energy.
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Understanding Organic Reactions
Use of Arrows:
• A number of types of arrows are used in describing organic
reactions.
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Understanding Organic Reactions
Bond Dissociation Energy:
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Understanding Organic Reactions
Bond Dissociation Energy:
• Comparing bond dissociation energies is equivalent to
comparing bond strength.
• The stronger the bond, the higher its bond dissociation
energy.
• Bond dissociation energies decrease down a column of the
periodic table.
• Generally, shorter bonds are stronger bonds.
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Understanding Organic Reactions
Bond Dissociation Energy:
• Bond dissociation energies are used to calculate the
enthalpy change (ΔH0) in a reaction in which several bonds
are broken and formed.
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Understanding Organic Reactions
Bond Dissociation Energy:
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Understanding Organic Reactions
Bond Dissociation Energy:
Bond dissociation energies have some important limitations.
• Bond dissociation energies present overall energy changes
only. They reveal nothing about the reaction mechanism or
how fast a reaction proceeds.
• Bond dissociation energies are determined for reactions in
the gas phase, whereas most organic reactions occur in a
liquid solvent where solvation energy contributes to the
overall enthalpy of a reaction.
• Bond dissociation energies are imperfect indicators of
energy changes in a reaction. However, using bond
dissociation energies to calculate ΔH° gives a useful
approximation of the energy changes that occur when
bonds are broken and formed in a reaction.
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Understanding Organic Reactions
Thermodynamics and Kinetics:
• For a reaction to be practical, the equilibrium must favor
products and the reaction rate must be fast enough to form
them in a reasonable time. These two conditions depend
on thermodynamics and kinetics respectively.
• Thermodynamics describes how the energies of reactants
and products compare, and what the relative amounts of
reactants and products are at equilibrium.
• Kinetics describes reaction rates.
• The equilibrium constant, Keq, is a mathematical expression
that relates the amount of starting material and product at
equilibrium.
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Understanding Organic Reactions
Thermodynamic Terms:
• ΔG° is the term for standard state free energy and represents
the overall energy difference between reactants (R) and
products (P).
• ΔH° is the term for enthalpy in the standard state.
• ΔS° is the term for entropy in the standard state.
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Understanding Organic Reactions
Thermodynamics:
• The size of Keq expresses whether the starting materials or
products predominate once equilibrium is reached.
• When Keq > 1, equilibrium favors the products (C and D) and
the equilibrium lies to the right as the equation is written. This
is a useful reaction.
• When Keq < 1, equilibrium favors the starting materials (A and
B) and the equilibrium lies to the left as the equation is
written.
• The position of the equilibrium is determined by the relative
energies of the reactants and products.
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Understanding Organic Reactions
Thermodynamics:
Figure 6.3 Summary of the relationship between ∆G° and Keq.
Note the use of base a 10 log vs a natural log in these equations.
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Understanding Organic Reactions
Thermodynamics:
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Understanding Organic Reactions
Thermodynamics:
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Understanding Organic Reactions
Thermodynamics:
• These equations can be used for any process with two states
in equilibrium. E.g., monosubstituted cyclohexanes exist as
two different chair conformations that rapidly interconvert at
room temperature and equatorial position favored.
• Knowing the energy difference between two conformations
permits the calculation of the amount of each at equilibrium.
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Understanding Organic Reactions
Enthalpy and Entropy:
• ΔG° depends both on ΔH° and ΔS°.
• Entropy change, ΔS°, is a measure of the change in the
randomness of a system. The more disorder present, the
higher the entropy.
• The value of ΔS° is (+) when the products are more
disordered than the reactants and (-) when the products
are less disordered than the reactants.
• Reactions resulting in increased entropy contribute to a
negative ΔG°.
• ΔG° is related to ΔH° and ΔS° by the following equation:
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Understanding Organic Reactions
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Understanding Organic Reactions
Enthalpy and Entropy:
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Understanding Organic Reactions
Energy Diagrams:
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Understanding Organic Reactions
Energy Diagrams:
• A diagram can also be made by plotting free energy.
Then energy difference between reactants and products
is ΔG°. If the products are lower in energy than the
reactants, the reaction is exergonic and energy is
released. If the products are higher in energy than the
reactants, the reaction is endergonic and energy is
required.
• The unstable energy maximum as a chemical reaction
proceeds from reactants to products is called the
transition state. The transition state species can never
be isolated.
• The energy difference between the transition state and
the starting material is called the energy of activation,
Ea.
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Understanding Organic Reactions
Energy Diagrams:
• For the general reaction:
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Understanding Organic Reactions
Energy Diagrams:
• The energy of activation is the minimum amount of energy
needed to break the bonds in the reactants.
• The larger the Ea, the greater the amount of energy that is
needed to break bonds, and the slower the reaction rate.
• The structure of the transition state is somewhere between
the structures of the starting material and product. Any
bond that is partially formed or broken is drawn with a
dashed line. Any atom that gains or loses a charge contains
a partial charge in the transition state.
• Transition states are drawn in brackets, with a superscript
double dagger (‡).
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Understanding Organic Reactions
Energy Diagrams:
Example 1
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Understanding Organic Reactions
Energy Diagrams:
Example 2
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Understanding Organic Reactions
Energy Diagrams:
Example 3
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Understanding Organic Reactions
Energy Diagrams:
Example 4
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Understanding Organic Reactions
Energy Diagrams:
Figure 6.5 Comparing ∆H° and Ea in two energy diagrams
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Understanding Organic Reactions
Energy Diagrams:
• Consider the following two step reaction:
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Understanding Organic Reactions
Energy Diagrams:
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Understanding Organic Reactions
Figure 6.6 Complete energy diagram for
Energy Diagrams: the two-step conversion of
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Understanding Organic Reactions
Kinetics:
• Kinetics is the study of reaction rates.
• Recall that Ea is the energy barrier that must be exceeded
for reactants to be converted to products.
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Understanding Organic Reactions
Kinetics:
• The higher the concentration, the faster the rate.
• The higher the temperature, the faster the rate.
• ΔG°, ΔH°, and Keq do not determine the rate of a reaction.
These quantities indicate the direction of the equilibrium
and the relative energy of reactants and products.
• A rate law or rate equation shows the relationship between
the reaction rate and the concentration of the reactants. It is
experimentally determined.
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Understanding Organic Reactions
Kinetics:
• Fast reactions have large rate constants.
• Slow reactions have small rate constants.
• The rate constant k and the energy of activation Ea are
inversely related. A high Ea corresponds to a small k.
• A rate equation contains concentration terms for all
reactants in a one-step mechanism but contains
concentration terms for only the reactants involved in the
rate-determining step in a multi-step reaction.
• The order of a rate equation equals the sum of the
exponents of the concentration terms in the rate equation.
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Understanding Organic Reactions
Kinetics:
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Understanding Organic Reactions
Catalysts:
• Some reactions do not proceed at a reasonable rate unless
a catalyst is added.
• A catalyst is a substance that speeds up the rate of a
reaction. It is recovered unchanged in a reaction, and it does
not appear in the product.
Figure 6.7 The effect of a catalyst on a reaction
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