ORGANIC CHEMISTRY Chemical Properties of Organic Compounds

ACIDS AND BASES

An understanding of the factors which influence the strength of organic acids and bases is fundamental to
a knowledge of other organic reactions.

The acidity constant Ka for any acid HA is the equilibrium constant for the following equation multiplied
by the molar concentration of water. The pKa is the negative log of the Ka value.

HA + H2O H3O+ + A–

Ka =[H3O+][A–] pKa = -log Ka

[HA]

In any equilibrium between an acid and a base, the equilibrium always lies toward the weaker acid and weaker
base.

There are five major influences on the acidity of organic compounds.

1. Electronegativity and Size of the Atom

In any row of the periodic table, acidities increase from left to right, paralleling electronegativity. But in
any column of the periodic table, the acidity increases from top to bottom, along with size.

(least acidic) CH4 50-60 NH3 35 H2O 16 HF 3

PH3 ? H2S 7 HCl –7
H2Se 4 HBr –9
HI –10 (most acidic)

2. Charge
Other things being equal, acidity increases with increasing positive charge.

3. Hybridization.
Acidity increases as the s character of the bond to hydrogen increases.

C-H N-H O-H

sp H-C≡C-H 25 + –10
R-C≡NH
+ +
sp 2
H2C=CH2 44 R2C=NHR 5 R2C=OH –7
+ +
sp3 CH3-CH3 60 R-NH3 10 R-OH2 –2

4. Aromaticity
Sometimes an acid-base reaction changes an aromatic compound into a non-aromatic compound, or vice
versa. This can have a very largeeffect on the observed acidity

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5. Substituents
Substituents which stabilize an anion enhance the acidity of the corresponding acid (HA). Note that the
acidities of water and alcohols are very similar, but compounds with electronegative groups attached to the
oxygen are considerably more acidic than water

X- X-CH3 X-NH2 X-OH (X-OH)

CF3SO2- -14 trifluoromethanesul
ArSO2- 23 -1 sulfonic acids
CF3-CO- 0.2 trifluoroacetic acid
Ph-CO- 4.2 benzoic acid
CH3-CO- 20 17 4.8 acetic acid
PNP- 7.1 p-nitrophenol
Ph- 41 27 10.0 phenol
H- 50-60 34 15.74 water
R- 50-60 35-40 16-19 alcohols

Lewis Acid and Bases

Lewis acids are electron pair acceptors

Lewis bases are electron pair donors.

When Lewis acids react with organic compounds, they are often referred to as electrophiles (electron
lovers).

When Lewis bases react with organic compounds, they are often called nucleophiles.

Organic compounds which behave as nucleophiles include alcohols, amines, organometallic compounds, and
unsaturated hydrocarbons.

Electron pushing.

Organic chemists often use curved arrows to indicate the flow of electrons in resonance structures or in
reactions.

Polarity of Functional Groups

Functional groups in which the carbon is bonded to an electronegative element such as oxygen or halogen
have a partial positive charge on the carbon and a partial negative charge on the heteroatom.

Functional groups in which the carbon is bonded to an electropositive element have apartial negative charge
on the carbon and a partial positive charge on the metal.

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Rates and Equilibria

The equilibrium constant for a reaction is related to the overall free energy change (ΔG), while therate is related
to the free energy of the transition state. This is sometimes shown graphically as a reaction energy diagram.

Bond Energies

The free energy of a reaction (∆G) is composed of entropy and enthalpy terms. The enthalpy term(the heat of
reaction, ∆H) is usually more important, and in many cases can be easily calculated.

There are four things you should know about halogenation reactions:

1. Alkanes react with Cl2 or Br2 (usually with heat or light) to give alkyl halides (haloalkanes).

2. The reaction mechanism involves free radicals.

3. In general the reaction gives a mixture of all possible isomers (without rearrangement). Consequently it is
nearly worthless as a synthetic method for making alkyl halides. However, the number of isomers formed
indicates the number of different kinds of hydrogen atoms in the molecule.

4. By careful measurement of heats of reaction, chemists have been able to calculate numerous bond energies.
And conversely, we can use bond energies to predict whether a halogenation reaction will be exothermic or
endothermic.

Bond dissociation energies (in kcal/mol)

H-H 104 CH3-H 105 CH3CH2-H 101 CH3CH2-Cl 85
H-Cl 103 CH3-Cl 84 (CH3)2CH-H 99 (CH3)2CH-Cl 85
H-Br 88 CH3-Br 72 (CH3)3C-H 97 (CH3)3CCl 85
Cl-Cl 58 CH3-OH 92 H2C=CH-H 111 H2C=CH-Cl 91
Br-Br 46 CH3-CH3 90 Ph-H 113 Ph-Cl 97

ORGANIC REACTIONS

Types of Reactions

There are several ways in which organic reactions can be classified. One way is to describe them aseither
polar, radical, or pericyclic. Of these three types, we will be primarily concerned with polar (ionic)
reactions.

Reactive Intermediate.
A number of polar reactions involve carbocations or carbanions. Radical reactions involve radicals. A few
reactions involve divalent carbon intermediates called carbenes.

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Substitution Reactions
In a substitution reaction, one atom or a group of atoms is substituted by another atom or a group of atoms to form
a new substance.

Elimination reaction
There are some reactions which involve the elimination or removal of the adjacent atoms or group of atoms. After
this multiple bonds are formed and there is a release of small molecules as products.

Addition reactions

An addition reaction occurs when two or more reactants combine to form a product without the loss of any atoms
present in the reactants. Addition reaction is common in compounds that have unsaturated C-C bonds, like double
(alkene) and triple (alkyne) bonds. The weaker π bond is converted into two new stronger σ bonds.

Radical reactions
Many of the organic reactions involve radicals. The addition of a halogen to a saturated hydrocarbon involves a
free radical mechanism.

Initially when the weak bond is broken initiation of the reaction takes place with the formation of free radicals.
After that when the halogen is added to the hydrocarbon a radical is produced and finally, it gives alkyl halide.

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