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Chlorination of Methane
Equations for organic reactions are usually drawn with a single reaction arrow ()
between the starting material and product.
The reagent, the chemical substance with which an organic compound reacts, is
sometimes drawn on the left side of the equation with the other reactants. At other times,
the reagent is drawn above the arrow itself.
Although the solvent is often omitted from the equation, keep in mind that most organic
reactions take place in liquid solvent.
The solvent and temperature of the reaction may be added above or below the arrow.
The symbols h and are used for reactions that require light and heat respectively.
When two sequential reactions are carried out without drawing any intermediate
compound, the steps are usually 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, not at the same time.
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.
In a general substitution, Y replaces Z on a carbon atom.
Elimination Reactions
Elimination is a reaction in which elements of the
starting material are lost and a bond is formed.
( X and Y are detached from two different carbon atoms that are vicinal to each other)
Addition Reactions
Addition reaction is the reaction in which elements are added to the
starting material.
( X and Y add to two different atoms in a molecule that has one or more bonds)
Practice Exercises
Classify the following rxns as substitution, elimination, or addition.
Carbocation Structure
Carbocation Stability
Free Radicals
Also electron-deficient.
Stabilized by alkyl substituents.
Order of stability:
3 > 2 > 1 > methyl
Carbanions
Eight electrons on carbon:
6 bonding plus one lone
pair.
Carbon has a negative
charge.
Destabilized by alkyl
substituents.
Methyl >1 > 2 > 3
Carbenes
Carbon is neutral.
Vacant p orbital, so can be electrophilic.
Lone pair of electrons, so can be nucleophilic.
a)
+ OH
OH
carbocation
b)
H3CH2C
Li
H3C
CH2
carbanion
Li
33
a)
b)
HO
OH
2 OH
c)
+ Br
Br
b)
c)
H3C
(H3C)2C
OH
H3C
H3C
SH
OCH3
Bond dissociation energies are used to calculate the enthalpy change (H0)
in a reaction in which several bonds are broken and formed.
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.
When Keq < 1, equilibrium favors the starting materials (A and B) and the equilibrium lies
to the left as the equation is written.
For a reaction to be useful, the equilibrium must favor the products, and Keq > 1.
The position of the equilibrium is determined by the relative energies of the reactants
and products.
G is the overall energy difference between reactants and products.
When Keq > 1, log Keq is positive, making G negative, and energy is released.
Thus, equilibrium favors the products when the energy of the products is lower than
the energy of the reactants.
When Keq < 1, log Keq is negative, making G positive, and energy is absorbed.
Thus, equilibrium favors the reactants when the energy of the products is higher
than the energy of the reactants.
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.
This equation indicates that the total energy change is due to two
factors: the change in bonding energy and the change in disorder.
The change in bonding energy can be calculated from bond
dissociation energies.
Entropy changes are important when
The number of molecules of starting material differs from the
number of molecules of product in the balanced chemical equation.
An acyclic molecule is cyclized to a cyclic one, or a cyclic molecule
is converted to an acyclic one.
In most other reactions that are not carried out at high temperature, the entropy term (TS) is
small compared to the enthalpy term (H0), and therefore it is usually neglected.
Factors Determining G
Free energy change depends on:
Enthalpy
H= (enthalpy of products) - (enthalpy of reactants)
Entropy
S = (entropy of products) - (entropy of reactants)
G = H - TS
Enthalpy
Ho = heat released or absorbed during a chemical reaction at
standard conditions.
Exothermic (-H) heat is released.
Endothermic (+H) heat is absorbed.
Reactions favor products with lowest enthalpy (strongest bonds).
Entropy
So = change in randomness, disorder, or freedom of movement.
Increasing heat, volume, or number of particles increases entropy.
Energy Diagrams
For the general reaction:
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 ().
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 products 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.
Ea is the energy barrier that must be
exceeded for reactants to be converted to
products.
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
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.
Catalysts
Some reactions do not proceed at a reasonable rate unless a catalyst is
added.
Changes the speed of a reaction
Changes the speed of a reaction: A catalyst is a substance that speeds up the
rate of a reaction.
Does not appear in the product: It is recovered unchanged in a reaction, and it
does not appear in the product
Many types of catalyst can easily be recovered and used again
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.
The effect of a catalyst on a reaction