Physical and Chemical

Properties Of Alcohols
 Introduction
 Alcohol is any compound in which a hydroxyl
functional group (-OH) is bound to a carbon atom.
 There are three classes (types) of alcohols:
primary
secondary
and tertiary
Primary Alcohol:
 In a primary (1°) alcohol, the carbon which
carries the -OH group is only attached to one
alkyl group.

General formula: RCH2OH

Primary Alcohol examples

Methanol Ethanol

Secondary Alcohol:
In a secondary (2°) alcohol, the carbon with the -OH
group attached is joined directly to two alkyl groups.

General formula: R2CHOH

Tertiary Alcohol:
In a tertiary (3°) alcohol, the carbon atom holding the -OH
group is attached directly to three alkyl groups.

General formula: R3COH

 Physical Properties of Alcohol
 Molecular state:
straight chain alcohols with up to 12 carbon atoms
are liquids.
 Solubility:
alcohols with a small organic part as methanol or
ethanol are much like water, thus miscible with
water.
 Alcohols with a larger molecular weight are more
like alkane and less like water.
Alcohols with more than two -OH groups are more
water soluble than similar alcohols with only one -
OH group.
 Physical Properties of Alcohol

In general each -OH group can solubilize four to five

carbon atoms.
For example: Glycerol

 Boiling point:
the boiling point of an alcohol is always much higher
than that of the alkane with the same number of carbon
atoms.
alcohols with two or more –OH groups have higher
boiling point.
 Physical Properties of Alcohol
Methanol, Ethanol and Glycerol:
Color colorless
Odor they have faint odor (alcoholic odor) except
glycerol which is odorless.
Solubility completely miscible with water.
Flammability flammable with blue, non smoky flame.
State liquid except glycerol which is viscous liquid.

Acid-base neutral
properties
 Chemical Properties of Alcohol

Oxidation:
 The oxidising agent used is a solution of potassium
dichromate (K2Cr2O7) acidified with sulphuric
acid (H2SO4).
 If oxidation occurs, the orange solution containing
the dichromate ions is reduced to a green solution
containing chromium ions.
 Reactions of Alcohols
• Conversion of alcohols into alkyl halides:
• 3˚ alcohols react with HCl or HBr by SN1 through
carbocation intermediate
• 1˚ and 2˚ alcohols converted into halides by
treatment with SOCl2 or PBr3 via SN2 mechanism
Reactions of 1˚ and 2˚ alcohols
 Dehydration of Alcohols to Yield Alkenes
• The general reaction: forming an alkene from an
alcohol through loss of O-H and H (hence
dehydration) of the neighboring C–H to give 
bond
• Specific reagents are needed
 Acid- Catalyzed Dehydration
• Tertiary alcohols are readily dehydrated with acid
• Secondary alcohols require severe conditions (75%
H2SO4, 100°C) - sensitive molecules do not survive
• Primary alcohols require very harsh conditions –
impractical
• Reactivity is the result of the nature of the carbocation
intermediate
Incorporation of Alcohols into Esters
 Oxidation of Alcohols
• Can be accomplished by inorganic reagents,
such as KMnO4, CrO3, and Na2Cr2O7 or by more
selective, expensive reagents
 Mechanism of Chromic Acid Oxidation
• Alcohol forms a chromate ester followed by
elimination with electron transfer to give
ketone
• The mechanism was determined by
observing the effects of isotopes on rates
 Introduction

Aldehydes are compounds of the general formula RCHO;

Ketones are compounds of the general formula RR´CO.
The groups R and R´ may be aliphatic or aromatic.

O O O
C C C
R H R R
Carbonyl group Aldehyde Ketone

Both aldehydes and ketones contain the carbonyl

group, C=O, and are often called carbonyl compounds.
 An aldehyde is often written as RCHO. Remember that
the H atom is bonded to the carbon atom, not the
oxygen.

 Likewise, a ketone is written as RCOR, or if both alkyl

groups are the same, R2CO.

 The three bonds (carbon, oxygen, and the two other

atoms attached to carbonyl carbon) lie in a plane; the
three bond angels of carbon are very close to 120º.
 Nomenclature
Both IUPAC and common names are used for
aldehydes and ketones.

 Naming Aldehydes in the IUPAC System

To name an aldehyde using the IUPAC system:
[1] If the CHO is bonded to a chain of carbons, find the
longest chain containing the CHO group, and change the -
e ending of the parent alkane to the suffix -al.
If the CHO group is bonded to a ring, name the ring and
add the suffix -carbaldehyde.

[2] Number the chain or ring to put the CHO group at C1

Give the IUPAC name for the compounds:
 Naming Ketones in the IUPAC System

 To name an acyclic ketone using IUPAC rules:

[1] Find the longest chain containing the carbonyl

group, and change the -e ending of the parent alkane
to the suffix -one.

[2] Number the carbon chain to give the carbonyl carbon

the lower number. Apply all of the other usual rules
of nomenclature.
 Physical properties:
Boiling point:

Aldehydes and ketones are polar compounds due to the

polarity of carbonyl group and hence they have higher
boiling points than non polar compounds of
comparable molecular weight.

 But they have lower boiling points than comparable

alcohols or carboxylic acids due to the intermolecular
hydrogen bonding.
Solubility:
The lower aldehydes and ketones soluble in
water, because of hydrogen bonding between
carbonyl group and water, also they soluble in
organic solvents.
 Reactions of Aldehydes and Ketones

Aldehydes and Ketones undergo many reactions to give a

wide variety of useful derivatives. There are two general
kinds of reactions that aldehydes and ketones undergo:

[1] Reaction at the carbonyl carbon (Nucleophilic addition

reactions).
[2] Reaction at the α carbon

A second general reaction of aldehydes and

ketones involves reaction at the α carbon. A C–H bond
on the α carbon to a carbonyl group is more acidic
than many other C–H bonds, because reaction with
base forms a resonance-stabilized enolate anion.
 Acid-catalyzed nucleophilic addition
The general mechanism for this reaction consists of three
steps (not two), but the same product results because H and Nu-
add across the carbonyl π bond. In this mechanism protonation
precedes nucleophilic attack.

Step [1] Protonation of the carbonyl group

In Step [2], the nucleophile attacks, and then deprotonation
forms the neutral addition product in Step [3].

Steps [2]–[3] Nucleophilic attack and deprotonation

a) Addition of Alcohols (Acetal Formation):

Aldehydes and ketones react with two equivalents of

alcohol to form acetals. In an acetal, the carbonyl
carbon from the aldehyde or ketone is now singly
bonded to two OR" (alkoxy) groups.
 b) Nucleophilic Addition of H- (Reduction reaction)

Treatment of an aldehyde or ketone with either Sodium

borohydride (NaBH4) or Lithium hydride (LiAlH4) followed by
protonation forms a 1° or 2° alcohol.
 Hydride reduction of aldehydes and ketones occurs via
the two-step mechanism of nucleophilic addition, that is,
nucleophilic attack of H:– followed by protonation.
c) Reduction to alkane (Deoxygenation of Ketones and Aldehydes):

i) Clemmensen reduction.
ii) Wolff–Kishner reduction.

Z n(H g ), co n c. H C l
C H C le m m e n se n red u ctio n
O
fo r c o m p o u n d s se n sitiv e to ba se
H

N H 2 N H 2 , base
C H W o lff-K ish n er r ed u ctio n
fo r c o m p o u n d s sen sitive to a cid
H
d) Nucleophilic Addition of CN– :
Treatment of an aldehyde or ketone with NaCN and
a strong acid such as HCl adds the elements of HCN
across the carbon–oxygen π bond, forming a
cyanohydrin.
Carboxylic Acids
Structure
• Carboxylic acid groups consist of two very
polar functional groups
– Carbonyl group
– Hydroxyl group
• Carboxylic acid groups are very polar
 Physical Properties
• Low molecular weight carboxylic acids
– Sharp, sour taste
– Unpleasant aromas
• High molecular weight carboxylic acids
– Fatty acids important in biochemistry
• Low molecular weight carboxylic acids are water
soluble due to hydrogen bonding with:
– Water
– Each other
 Physical Properties
• Carboxylic acids exhibit dipole-dipole interactions
because they have polar C—O and O—H bonds.
• They also exhibit intermolecular hydrogen bonding.
• Carboxylic acids often exist as dimers held together by
two intermolecular hydrogen bonds.

Two molecules of acetic acid

(CH3COOH) held together by
two hydrogen bonds

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 Physical Properties
Due to carboxylic acids forming intermolecular
hydrogen bonds boiling points are at higher
temperatures than those of any other functional
group studied
Nomenclature—The IUPAC System

• In the IUPAC system, carboxylic acids are identified

by a suffix added to the parent name of the longest
chain with different endings being used depending
on whether the carboxy group is bonded to a chain
or a ring.
If the COOH is bonded to a chain, find the longest
chain containing the COOH, and change the “e” ending
of the parent alkane to the suffix “oic acid”.
If the COOH is bonded to a ring, name the ring and add
the words “carboxylic acid”.
Number the carbon chain or ring to put the COOH
group at C1, but omit this number from the name.
Apply all the other usual rules of nomenclature.
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• Compounds containing two carboxy groups are called
diacids. Diacids are named using the suffix –dioic acid.

• Metal salts of carboxylate anions are formed from

carboxylic acids in many reactions. To name the metal
salt of a carboxylate anion, put three parts together:

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 Reactions of Carboxylic Acids

The most important reactive feature of a

carboxylic acid is its polar O—H bond, which is
readily cleaved with base.

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• The non-bonded electron pairs on oxygen create
electron-rich sites that can be protonated by strong
acids (H—A).
• Protonation occurs at the carbonyl oxygen because
the resulting conjugate acid is resonance stabilized
(Possibility [1]).
• The product of protonation at the OH group (Possibility
[2]) cannot be resonance stabilized.

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• The polar C—O bonds make the carboxy carbon
electrophilic. Thus, carboxylic acids react with
nucleophiles.
• Nucleophilic attack occurs at an sp2 hybridized carbon
atom, so it results in the cleavage of the  bond as well.

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 Carboxylic Acids—Strong Organic BrØnsted-
Lowry Acids

• Carboxylic acids are strong organic acids, and as such,

readily react with BrØnsted-Lowry bases to form
carboxylate anions.
• An acid can be deprotonated by a base that has a conjugate acid
with a higher pKa.
• Because the pKa values of many carboxylic acids are ~5, bases
that have conjugate acids with pKa values higher than 5 are
strong enough to deprotonate them.

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44
• Carboxylic acids are relatively strong acids because
deprotonation forms a resonance-stabilized conjugate
base—a carboxylate anion.

• The acetate anion has two C—O bonds of equal length

(1.27 Å) and intermediate between the length of a C—O
single bond (1.36 Å) and C=O (1.21 Å).

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• Resonance stabilization accounts for why carboxylic acids
are more acidic than other compounds with O—H bonds—
namely alcohols and phenols.

• To understand the relative acidity of ethanol, phenol and

acetic acid, we must compare the stability of their
conjugate bases and use the following rule:
- Anything that stabilizes a conjugate base A:¯ makes the
starting acid H—A more acidic.
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