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Understanding Organic Reactions Writing Equations For Organic Reactions
Understanding Organic Reactions Writing Equations For Organic Reactions
Figure 6.1
Different ways of writing
organic reactions
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OH
Br
substitution
b)
addition
c)
elimination
OH
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To illustrate the movement of a single electron, use a halfheaded curved arrow, sometimes called a fishhook.
A full headed curved arrow shows the movement of an
electron pair.
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Figure 6.2
Three reactive intermediates
resulting from homolysis and
heterolysis of a C Z bond
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OH
carbocation
b)
H3CH2C
Li
H3C
CH2
Li
carbanion
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b)
HO
OH
2 OH
c)
+
Br
Br
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b)
c)
H3C
(H3C)2C
OH
H3C
H3C
SH
OCH3
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CH4 + 2O2
Bonds Broken
CO2 + 2H2O
Bonds Formed
= 238 kcal/mol
H = 416 + 238 =
+654 kcal/mol
H = -256 + -476 =
-732 kcal/mol
Thermodynamics
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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Figure 6.3
Summary of the
relationship
between G and Keq
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These equations can be used for any process with two states in
equilibrium. As an example, monosubstituted cyclohexanes exist
as two different chair conformations that rapidly interconvert at
room temperature, with the conformation having the substituent
in the roomier equatorial position favored.
Knowing the energy difference between two conformations
permits the calculation of the amount of each at equilibrium.
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Energy Diagrams
An energy diagram is a schematic representation of the energy
changes that take place as reactants are converted to products.
An energy diagram plots the energy on the y axis versus the
progress of reaction, often labeled as the reaction coordinate, on
the x axis.
The energy difference between reactants and products is H. If
the products are lower in energy than the reactants, the reaction
is exothermic and energy is released. If the products are higher
in energy than the reactants, the reaction is endothermic and
energy is consumed.
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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Figure 6.4
Some representative
energy diagrams
Example 1
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Figure 6.4
Some representative
energy diagrams
Example 2
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Figure 6.4
Some representative
energy diagrams
Example 3
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Figure 6.4
Some representative
energy diagrams
Example 4
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Figure 6.5
Comparing H and Ea in two
energy diagrams
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Figure 6.6
Complete energy diagram for
the two-step conversion of
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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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Kinetics
The higher the concentration, the faster the rate.
The higher the temperature, the faster the rate.
G, H, 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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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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