M O D U L A R S Y S T E M

OXYGEN and NITROGEN

containing
ORGANIC COMPOUNDS

Ayhan NAZLI
Murat DURKAYA
Yener EKÞÝ
Nuh ÖZDÝN
Muhammet AYDIN
Davut PÝRAZ
Necdet ÇELÝK
Uður Hulusi PATLI
Varol GÜRLER

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 Chemistry is an interesting and fundamental branch of science because
it gives us the chance to explain the secrets of nature. What is water? What
do we use in our cars as fuel? What is aspirin? What are perfumes made of?
Many of these kinds of questions and their answers are all part of the world
of chemistry. There is no industry that does not depend upon chemical sub-
stances; petroleum, pharmaceutical, garment, aircraft, steel, electronics,
agricultural, etc. This book helps everyone to understand the chemistry in
nature. However, one does not need to be a chemist or scientist to under-
stand the simplicity within the complexity around us.
The aim was to write a modern, up-to-date book where students and
teachers can find concise information about the structure of substances.
Sometimes reactions are given in detailed form, but, in all, excessive detail
has been omitted.
The book is designed to introduce basic knowledge about organic com-
pounds containing oxygen and nitrogen. Chemists work everyday to pro-
duce new compounds to make our lives easier with the help of this basic
knowledge. In the design, emphasis has been placed upon making the
book student friendly. Throughout the books, colorful tables, important reac-
tions, funny cartoons, interesting extras and reading passages are used to
help explain ideas. This book will also show you how many organic com-
pounds are important to us in our everyday lives. We hope that after study-
ing this book you will find organic chemistry in every part of your life.
The authors would like to thank Orhan Keskin, Ali Çavdar and Ramazan
Þahin for their support and encouragement throughout the development of
this book.
We would also like to thank Tekin Çorbalý, Mustafa Yýlmaz and Okan
Çeliker for their thoughtful criticisms and helpful suggestions to the manu-
script which have been of such great value in developing the book.
Many people have assisted us in writing these books. We wish to grate-
fully acknowledge the contributions of Þerafettin Küçükoðlu, Faik Bolat and
Sani Demiri for their reviews and suggestions.
We are particularly grateful to our spouses and children for their
patience during the writing of the book.

The Authors
Chapter 1
ALCOHOLS AND ETHERS
INTRODUCTION TO ALCOHOLS . . . . . . . . . . . . . . . 10
1. CLASSIFICATION OF ALCOHOLS . . . . . . . . . . 12
1.1. ACCORDING TO THE NUMBER OF
– OH GROUP . . . . . . . . . . . . . . . . . . . . . . . . 12
Monohydric Alcohols . . . . . . . . . . . . . . . . . . . . . . 12
Polyhydric Alcohols . . . . . . . . . . . . . . . . . . . . . . . 12
1.2. ACCORDING TO THE CARBON
ATOM HAVING THE –OH GROUP . . . . . . . 12
Primary (1°) Alcohols . . . . . . . . . . . . . . . . . . . . . . 12
Secondary (2°) Alcohols . . . . . . . . . . . . . . . . . . . . 13
Tertiary (3°) Alcohols . . . . . . . . . . . . . . . . . . . . . . . 13
2. NOMENCLATURE OF ALCOHOLS . . . . . . . . . . 13
2.1. COMMON NAMES . . . . . . . . . . . . . . . . . . . 13
2.2. USING THE IUPAC SYSTEM . . . . . . . . . . . 14
3. PHYSICAL PROPERTIES OF ALCOHOLS . . . . 17
4. CHEMICAL PROPERTIES ALCOHOLS . . . . . . . 22
4.1. REACTIONS OF ALCOHOLS INVOLVING
O–H BOND BREAKAGE . . . . . . . . . . . . . . . 22
Reaction of Alcohol with Alkali Metals . . . . . . . . . 23
Esterification Reactions . . . . . . . . . . . . . . . . . . . . 25
4.2. REACTIONS OF ALCOHOLS INVOLVING
C–O BOND BREAKAGE . . . . . . . . . . . . . . . 27
Reaction of Alcohols with Hydrogen Halides . . . 28
Dehydration of Alcohols . . . . . . . . . . . . . . . . . . . . 29
4.3. OXIDATION OF ALCOHOLS. . . . . . . . . . . . 31
Oxidation of Primary Alcohols . . . . . . . . . . . . . . . 32
Oxidation of Secondary Alcohols. . . . . . . . . . . . . 32
Oxidation of Tertiary Alcohols. . . . . . . . . . . . . . . . 32
4.4. COMBUSTION REACTIONS OF
ALCOHOLS . . . . . . . . . . . . . . . . . . . . . . . . . 35
5. PREPARATION OF ALCOHOLS. . . . . . . . . . . . . 36
5.1. SYNTHESIS OF ALCOHOLS FROM
ALKENES . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.2. SYNTHESIS OF ALCOHOLS FROM
ALKYL HALIDES . . . . . . . . . . . . . . . . . . . . . . . . . 37
5.3. SYNTHESIS OF ALCOHOLS BY
THE REDUCTION OF ALDEHYDES,
KETONES AND CARBOXYLIC ACIDS . . . 37
5.4. SYNTHESIS OF ALCOHOLS USING
GRIGNARD REAGENTS . . . . . . . . . . . . . . . 37
6. SOME IMPORTANT ALCOHOLS . . . . . . . . . . . . 39
6.1. METHYL ALCOHOL . . . . . . . . . . . . . . . . . . 39
Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . 39
Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . 40
Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
6.2. ETHYL ALCOHOL . . . . . . . . . . . . . . . . . . . . 41
Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . 41
Chemical Properties . . . . . . . . . . . . . . . . . . . . . . . 42
Synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
6.3. GLYCOL . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Reading : Life in the Poles . . . . . . . . . . . . . . . . . . 46
6.4. GLYCERINE . . . . . . . . . . . . . . . . . . . . . . . . . 47
7. INTRODUCTION TO ETHERS . . . . . . . . . . . . . . 47
8. NOMENCLATURE OF ETHERS . . . . . . . . . . . . . 49
8.1. COMMON NAMES . . . . . . . . . . . . . . . . . . . 49
8.2. IUPAC SYSTEM . . . . . . . . . . . . . . . . . . . . . . 50
9. PHYSICAL PROPERTIES OF ETHERS . . . . . . . 50
10. CHEMICAL PROPERTIES OF ETHERS . . . . . . 52
11. PREPARATION OF ETHERS . . . . . . . . . . . . . . . 53
Dehydration of Alcohols . . . . . . . . . . . . . . . . . . . . 53
The Williamson Synthesis of Ethers. . . . . . . . . . . 54
12. DIETHYL ETHER . . . . . . . . . . . . . . . . . . . . . . . . . 54
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . . . 55
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . . . 58
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Chapter 2
ALDEHYDES AND KETONES
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
1. ALDEHYDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2. NOMENCLATURE OF ALDEHYDES . . . . . . . . . 65
3. PHYSICAL PROPERTIES OF ALDEHY-
DES 67
4. CHEMICAL PROPERTIES OF ALDEHY-
DES 68
4.1. OXIDATION REACTIONS . . . . . . . . . . . . . . 68
Tollens’ Test (Silver Mirror Test) . . . . . . . . . . . . . . 69
Fehling’s Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Reactions with KMnO4 . . . . . . . . . . . . . . . . . . . . . 72
4.2. ADDITION REACTIONS OF ALDEHY-
DES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Addition of Hydrogen . . . . . . . . . . . . . . . . . . . . . . 73
Addition of Water . . . . . . . . . . . . . . . . . . . . . . . . . 74
Addition of Alcohol . . . . . . . . . . . . . . . . . . . . . . . . 75
Addition of HCN . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Addition of Grignard Reagents. . . . . . . . . . . . . . . 76
Addition of NaHSO3 . . . . . . . . . . . . . . . . . . . . . . . 77
4.3. POLYMERISATION . . . . . . . . . . . . . . . . . . . 78
4.4. COMBUSTION REACTION . . . . . . . . . . . . . 78
5. PREPARATION OF ALDEHYDES . . . . . . . . . . . 79
5.1. OXIDATION OF PRIMARY ALCO-
HOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.2. DEHYROGENATION OF PRIMARY ALCO-
HOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
6. SOME IMPORTANT ALDEHYDES . . . . . . . . . . . 81
6.1. FORMALDEHYDE . . . . . . . . . . . . . . . . . . . . 81
6.2. ACETALDEHYDE . . . . . . . . . . . . . . . . . . . . . 83
7. KETONES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
8. NOMENCLATURE OF KETONES. . . . . . . . . . . . 85
8.1. COMMON NAMES . . . . . . . . . . . . . . . . . . . 85
8.2. USING THE IUPAC SYSTEM . . . . . . . . . . . 85
9. PHYSICAL PROPERTIES OF KETONES . . . . . 86
10. CHEMICAL PROPERTIES OF KETONES . . . . . 88
10.1. ADDITION REACTIONS . . . . . . . . . . . . . 88
Addition of Hydrogen (Reduction of Ketones). . . 88
Addition of Water . . . . . . . . . . . . . . . . . . . . . . . . . 88
Addition of Alcohol . . . . . . . . . . . . . . . . . . . . . . . . 89
Addition of HCN . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Addition of Grignard Reagents. . . . . . . . . . . . . . . 90
Addition of NaHSO3 . . . . . . . . . . . . . . . . . . . . . . . 90
10.2. COMBUSTION REACTION . . . . . . . . . . . . 95
11. PREPARATION OF KETONES . . . . . . . . . . . . . 95
11.1. OXIDATION OF SECONDARY ALCO-
HOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
11.2. DEHYDROGENATION OF SECONDARY
ALCOHOLS . . . . . . . . . . . . . . . . . . . . . . . . . 96
11.3. HEATING CALCIUM SALTS OF CAR-
BOXYLIC ACIDS. . . . . . . . . . . . . . . . . . . . . 96
11.4. ADDITION OF WATER TO ALKYNES . . . . 96
12. ACETONE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
12.1. PREPARATION OF ACETONE . . . . . . . . . 97
Distillation of Wood. . . . . . . . . . . . . . . . . . . . . . . . 97
Heating of Calcium Acetate. . . . . . . . . . . . . . . . . 97
Oxidation of Isopropyl Alcohol . . . . . . . . . . . . . . . 97
From Acetic Acid . . . . . . . . . . . . . . . . . . . . . . . . . 98
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . . . 99
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . . 102
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Chapter 3
CARBOXYLIC ACIDS
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . .108
1. CLASSIFICATION OF CARBOXYLIC ACIDS .108
1.1. ACCORDING TO NUMBER OF
CARBOXYL GROUPS . . . . . . . . . . . . . . . .108
Monocarboxylic Acids . . . . . . . . . . . . . . . . . . . .108
Polycarboxylic Acids . . . . . . . . . . . . . . . . . . . . . .108
1.2. ACCORDING TO THE FUNCTIONAL
GROUPS . . . . . . . . . . . . . . . . . . . . . . . . . . .109
Hydroxy Acids . . . . . . . . . . . . . . . . . . . . . . . . . . .109
Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
Keto Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
2. NOMENCLATURE OF CARBOXYLIC
ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
2.1. COMMON NAMES . . . . . . . . . . . . . . . . . .109
2.2. USING THE IUPAC SYSTEM . . . . . . . . . .110
3. PHYSICAL PROPERTIES OF CARBOXYLIC
ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .112
4. CHEMICAL PROPERTIES OF CARBOXYLIC
ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .116
4.1. REACTION INVOLVING CLEAVAGE
OF THE O–H BOND . . . . . . . . . . . . . . . . .116
Salt Formation . . . . . . . . . . . . . . . . . . . . . . . . . . .116
Neutralization Reactions . . . . . . . . . . . . . . . . . . .117
Reactions with Salts . . . . . . . . . . . . . . . . . . . . . .118
4.2. REACTIONS THAT INVOLVE C–O
BOND BREAKAGE . . . . . . . . . . . . . . . . . .119
Formation of Acid Anhydrides . . . . . . . . . . . . . .119
Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . .120
Formation of Acid Chlorides . . . . . . . . . . . . . . . .121
4.3. ADDITION OF HALOGENS . . . . . . . . . . . .122
4.4. REDUCTION REACTIONS . . . . . . . . . . . .122
5. PREPARATION OF CARBOXYLIC ACIDS . . . .123
5.1. OXIDATION OF PRIMARY ALCOHOLS
AND ALDEHYDES . . . . . . . . . . . . . . . . . . .123
5.2. OXIDATION OF AROMATIC
COMPOUNDS . . . . . . . . . . . . . . . . . . . . . .123
5.3. OXIDATION OF ALKENES . . . . . . . . . . . .124
5.4. CARBONATION OF GRIGNARD
REAGENTS . . . . . . . . . . . . . . . . . . . . . . . .124
5.5. HYDROLYSIS OF CARBOXYLIC ACID
DERIVATIVES . . . . . . . . . . . . . . . . . . . . . . .124
5.6. HYDROLYSIS OF NITRILES . . . . . . . . . . .125
5.7. REACTION OF CARBOXYLATE
SALTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . .125
6. SOME IMPORTANT CARBOXYLIC ACIDS . . .126
6.1. FORMIC ACID . . . . . . . . . . . . . . . . . . . . . .126
Physical Properties . . . . . . . . . . . . . . . . . . . . . . .126
Chemical Properties . . . . . . . . . . . . . . . . . . . . . .126
Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .127
Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .128
6.2. ACETIC ACID . . . . . . . . . . . . . . . . . . . . . . .128
Physical Properties . . . . . . . . . . . . . . . . . . . . . . .128
Chemical Properties . . . . . . . . . . . . . . . . . . . . . .128
Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129
Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .130
Reading : Unsaturated Carboxylic Acids
and Their Polymers . . . . . . . . . . . . .130
7. DICARBOXYLIC ACIDS . . . . . . . . . . . . . . . . . .132
7.1. OXALIC ACID . . . . . . . . . . . . . . . . . . . . . . .132
Physical Properties . . . . . . . . . . . . . . . . . . . . . . .132
Chemical Properties . . . . . . . . . . . . . . . . . . . . . .132
Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .133
Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .133
7.2. MALONIC ACID . . . . . . . . . . . . . . . . . . . . .133
7.3. ADIPIC ACID . . . . . . . . . . . . . . . . . . . . . . .134
8. FATTY ACID . . . . . . . . . . . . . . . . . . . . . . . . . . . .134
8.1. SATURATED FATTY ACIDS . . . . . . . . . . .135
Palmitic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . .135
Stearic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135
 8.2. UNSATURATED FATTY ACIDS . . . . . . . .135
Oleic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .135
Linoleic Acid and Linolenic Acid . . . . . . . . . . . .135
9. OXYACIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . .136
Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .137
Carbonic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . .137
10. OPTICAL ISOMERISM . . . . . . . . . . . . . . . . . . .138
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . .142
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . .147
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .152
Chapter 4
ESTERS
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
1. ESTERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154
2. NOMENCLATURE OF ESTERS . . . . . . . . . . . .154
3. PHYSICAL PROPERTIES OF ESTER . . . . . . .156
4. CHEMICAL PROPERTIES OF ESTERS . . . . . .158
4.1. HYDROLYSIS OF ESTERS . . . . . . . . . . . .158
4.2. SAPONIFICATION OF ESTERS . . . . . . . .158
4.3. REDUCTION OF ESTERS . . . . . . . . . . . . .158
4.4. REACTION WITH AMMONIA . . . . . . . . . .159
5. PREPARATION OF ESTERS . . . . . . . . . . . . . . .160
5.1. FROM CARBOXYLIC ACID AND
ALCOHOLS . . . . . . . . . . . . . . . . . . . . . . . .160
5.2. FROM CARBOXYLIC ACID
DERIVATIVES . . . . . . . . . . . . . . . . . . . . . . .161
6. FATS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .162
6.1. CLASSIFICATION OF FATS . . . . . . . . . . .163
Vegetable Fats . . . . . . . . . . . . . . . . . . . . . . . . . .163
Animal Fats . . . . . . . . . . . . . . . . . . . . . . . . . . . . .163
According to Their Physical States . . . . . . . . . .163
7. HYDROGENATION AND MARGARINES . . . . .164
8. SAPONIFICATION . . . . . . . . . . . . . . . . . . . . . .165
9. CLEANING PROCESS OF SOAPS . . . . . . . . .166
10. DETERGENTS . . . . . . . . . . . . . . . . . . . . . . . . . .167
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . .168
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . .172
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .174
Chapter 5
CARBOHYDRATES
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . .176
1. STRUCTURE OF CARBOHYDRATES . . . . . . .176
2. NOMENCLATURE OF CARBOHYDRATES . . .177
3. CLASSIFICATION OF CARBOHYDRATES . . .178
3.1. MONOSACCHARIDES . . . . . . . . . . . . . . .178
General Properties . . . . . . . . . . . . . . . . . . . . . . .178
Cyclic Structures of Monosaccharides . . . . . . .179
Oxidation of Monosaccharides . . . . . . . . . . . . . .180
Reduction of Monosaccharides . . . . . . . . . . . . .184
3.2. DISACCHARIDES . . . . . . . . . . . . . . . . . . .186
General Properties . . . . . . . . . . . . . . . . . . . . . . .186
Saccharose (Sucrose) . . . . . . . . . . . . . . . . . . . .186
Lactose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .187
Maltose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .187
Cellobiose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .188
3.3. POLYSACCHARIDES . . . . . . . . . . . . . . . .188
General Properties . . . . . . . . . . . . . . . . . . . . . . .188
Starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .189
Glycogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .189
Dextrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .189
Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .190
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . .191
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . .193
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196
Chapter 6 Trinitrotoluene . . . . . . . . . . . . . . . . . . . . . . . . . . .220

AMINES, AMIDES AND AMINO ACIDS 3. AROMATIC AMINO COMPOUNDS . . . . . . . . .221

INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . .198
1. AMINES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .198
1.1. NOMENCLATURE OF AMINES . . . . . . . .198
Common Names . . . . . . . . . . . . . . . . . . . . . . . . .198
1.2. PHYSICAL PROPERTIES . . . . . . . . . . . . .201
1.3. CHEMICAL PROPERTIES AND
REACTIONS . . . . . . . . . . . . . . . . . . . . . . . .202
1.4. PREPARATION OF AMINES . . . . . . . . . . .203
2. AMIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .204
2.1. NOMENCLATURE OF AMIDES . . . . . . . .205
2.2. PROPERTIES OF AMIDES . . . . . . . . . . . .205
2.3. PREPARATION OF AMIDES . . . . . . . . . . .205
2.4. UREA (Carbamide) . . . . . . . . . . . . . . . . . .207
3. AMINO ACIDS . . . . . . . . . . . . . . . . . . . . . . . . . .207
3.1. NOMENCLATURE OF AMINO ACIDS . . .207
3.2. PROPERTIES OF AMINO ACIDS . . . . . . .208
4. PEPTIDE FORMATION AND PROTEINS . . . . .208
Reading : Chemistry of Vision . . . . . . . . . . . . .209
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . .210
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . .211
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .214
3.1. ANILINE . . . . . . . . . . . . . . . . . . . . . . . . . . .221
Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . .222
4. AROMATIC ALCOHOLS . . . . . . . . . . . . . . . . . .223
4.1. BENZYL ALCOHOL . . . . . . . . . . . . . . . . . .223
Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . .223
5. AROMATIC ALDEHYDES . . . . . . . . . . . . . . . . .225
5.1. BENZALDEHYDE . . . . . . . . . . . . . . . . . . . .225
Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .225
6. AROMATIC CARBOXYLIC ACIDS . . . . . . . . . .226
6.1. BENZOIC ACID . . . . . . . . . . . . . . . . . . . . .227
Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .227
6.2. TEREPHTHALIC ACID . . . . . . . . . . . . . . .228
SUPPLEMENTARY QUESTIONS . . . . . . . . . . . . . .229
MULTIPLE CHOICE QUESTIONS . . . . . . . . . . . . . .232
PUZZLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .238
GLOSSARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .240
ANSWERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .243
INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .255
REFERENCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .256

Chapter 7

AROMATIC COMPOUNDS
1. PHENOLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .216
1.1. PHENOL . . . . . . . . . . . . . . . . . . . . . . . . . . .216
2. AROMATIC NITRO COMPOUNDS . . . . . . . . . .218
2.1. GENERAL STRUCTURE . . . . . . . . . . . . . .218
2.2. NITRATION . . . . . . . . . . . . . . . . . . . . . . . . .219
Nitrobenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . .219
Dinitrobenzene . . . . . . . . . . . . . . . . . . . . . . . . . .220
 INTRODUCTION TO ALCOHOLS
Alcohols are compounds whose molecules have a hydroxyl group ( OH)
attached to a saturated carbon atom. Alcohols can be described as alkyl deriva-
tives of water where one hydrogen in the water molecule has been replaced by
an alkyl (R ) group. The general formula of alcohols is R OH and the gener-
al molecular formula of alcohols is CnH2n+1OH or CnH2n+2O.

R H H OH R OH
Alkane Water Alcohol
Although hundreds of alcohols are
known. When alcohol as a word is used The functional group that determines an alcohol is OH. The carbon atom
many people associate it only with ethyl having the OH group is attached to another carbon atom by a single bond
alcohol (ethanol). and is sp3 hybridised. The carbon chain of the rest of the alcohol can be saturat-
ed or unsaturated.

The saturated carbon atom having the OH group may:

a. be a carbon atom of a simple alkyl group, as in the following examples.

CH3 CH CH3
CH3 OH OH
OH
methyl alcohol cyclopentyl alcohol isopropyl alcohol

b. be from an alkenyl or alkynyl group, or it may be a saturated carbon atom

attached to a benzene ring as in the following examples.

CH2 CH CH2 OH CH C CH2 OH CH2OH

propenyl alcohol propynyl alcohol benzyl alcohol

Blood Alcohol Level Affects on The Body and Behavior!

The effects of drinking alcoholic Blood Alcohol Level Effect

beverages depend upon the
amount of actual ethyl alcohol
consumed and body weight. The
level of alcohol in the blood is cal-
culated in miligrams of pure ethyl
alcohol per deciliter of blood and
is commonly expressed as a per-
centage.
0.02 – 0.02% Changes in behavior and ability to think clearly
0.05% Sedation and tranquilized feeling
0.08 – 0.10% Legal intoxication in some countries.
0.15 – 0.20% Person is obviously intoxicated and may show signs of delirium
0.30 – 0.40% Loss of consciousness
Heart and respiration become so depressed that they cease to
0.50%
function and death follows

10 Oxygen And Nitrogen Containing Organic Compounds

 Compounds That Do Not Exhibit
The Properties of Alcohols
d. CH3COOH
Some compounds having the OH group do not show the
properties of alcohols. e. OH
1. Compounds in which the carbon atom bearing the
hydroxyl group is attached to a carbon atom with a dou-
f. OH
ble bond are called enols. Enols do not exhibit the prop-
erties of alcohols.
The compound in which the hydroxyl group is attached to a Solution
benzene ring is called phenol. ——————————————————————————
a. CH2 CH CH2 OH is an alcohol because the car-
CH3 CH CH CH2 CH OH bon atom attached to the OH group is saturated.
OH OH b. Since the OH groups are attached to different sat-
1 – propenol ethenol phenol urated carbon atoms, the compound
HO CH2 CH2 OH is an alcohol.
2. The carbon atom bearing the OH O
group in carboxylic acids is not satu- c. Since the OH groups are attached to the same
R CH2 C
rated. Carboxylic acids do not show carbon atom, the compound HO CH2 OH is not
OH
properties of alcohols. an alcohol. It is an aldehyde hydrate.
carboxylic acid
O
d. The structural formula of CH3COOH is
3. In a molecule, if the same carbon atom has more than CH3 C
one OH group it is not an alcohol.
OH
The molecule in which one carbon atom has two OH
groups is called an aldehyde hydrate or a ketone hydrate. If In this structure, the carbon atom that has the OH
the carbon atom has three OH groups it is called a car- group is also bonded to oxygen with a double bond
boxylic acid hydrate. and is therefore unsaturated. So CH3COOH is not an
OH OH OH alcohol, it is a carboxylic acid.
e. OH is an alcohol because the carbon atom
C OH CH2 C CH2 C OH

H OH OH that has theCH2 OH

OH group is saturated, having the
aldehyde ketone carboxylic structure C
hydrate hydrate acid hydrate
CH2 H

Example f. OH is not an alcohol because the carbon

——————————————————————————
Which of the following do not show the properties of an atom with the OH group has a double bond.
alcohol?
a. CH2 CH CH2 OH
b. HO CH2 CH2 OH
c. HO CH2 OH

Alcohols and Ethers 11

 1. CLASSIFICATION OF ALCOHOLS
Alcohols can be classified in two ways. The first classification is based on the
number of hydroxyl groups in the molecule, the second is based on the condi-
tion of the carbon atom with the hydroxyl group.

1.1. ACCORDING TO THE NUMBER OF — OH GROUPS

Alcohols can be classified as monohydric and polyhydric alcohols according to
the number of OH groups in their structure.

Monohydric Alcohols
Alcohols containing only one hydroxyl group in their structure are called mono-
hydric alcohols.
CH3

CH3 OH CH3 CH2 OH CH3 CH CH2 OH

methyl alcohol ethyl alcohol isobutyl alcohol

Polyhydric Alcohols
Alcohols containing two or more hydroxyl groups in their molecules are called
polyhydric alcohols. Alcohols containing two OH groups are called glycols
or diols, and those with three OH groups are called glycerols or triols.
CH2 CH2 CH2 CH2 CH2 CH2 CH CH2

OH OH OH OH OH OH OH
1, 2 - ethanediol 1, 3 - propanediol 1, 2, 3 - propanetriol
glycol trimethylene glycol glycerol

1.2. ACCORDING TO THE CARBON ATOM HAVING THE

— OH GROUP
Alcohols can be classified as primary, secondary and tertiary alcohols according
to the condition of the carbon atom to which the hydroxyl group is attached.

Primary (1°) Alcohols

H If the carbon bearing the OH group is attached to only one other carbon, that
H C OH carbon is said to be a primary carbon and the alcohol is a primary alcohol.

H Primary alcohols can be represented as:

H
CH3 OH
R C OH or R CH2 OH
(primary) methyl alcohol
H
Methyl alcohol which has only one car-
bon atom is considered a primary alco- Some examples for primary alcohols are given below:
hol.

12 Oxygen And Nitrogen Containing Organic Compounds

 H H H CH2 CH2

CH3 C OH CH3 CH2 C OH CH3 CH2 CH2 C OH OH OH

H H H In a glycol molecule each carbon atom

ethyl alcohol primary propyl alcohol primary butyl alcohol is a primary carbon and accordingly the
compound is a primary alcohol.
Secondary (2°) Alcohols
If the carbon with the OH group is attached to two other carbon atoms it is CH3 CH CH2
called a secondary carbon and the alcohol is a secondary alcohol. An alcohol OH OH
needs at least three carbon atoms to be secondary. (2) (1)

R¢ CH3 CH3 The 1, 2 – propanediol molecule is a pri-

mary alcohol with respect to the first
R C OH CH3 C OH CH3 CH2 C OH
OH group, but a secondary alcohol with
H H H respect to the second OH group.
secondary alcohol secondary propanol secondary butanol

Tertiary (3°) Alcohols

If the carbon having the OH group is attached to three other carbon atoms it
is called a tertiary carbon, and the alcohol is tertiary alcohol. In a tertiary alcohol,
there are at least four carbon atoms.

R¢ CH3 CH3

R C OH CH3 C OH CH3 CH2 C OH

R¢¢ CH3 CH3

tertiary alcohol tertiary butanol tertiary pentanol

Polyalcohols may be a combination of primary, secondary and tertiary depend-

ing on the positioning of each OH group.

2. NOMENCLATURE OF ALCOHOLS
2.1. COMMON NAMES
These are generally used for the simpler molecules of alcohols. Common names
Abbreviations in naming alcohols.
of alcohols are derived by naming the alkyl group attached to the OH group
Secondary = sec.
and then the word “alcohol” is added. The prefixes primary, secondary and terti-
Tertiary = tert.
ary may also be used.

CH3 OH C2H5 OH C3H7 OH C4H9 OH

methyl alcohol ethyl alcohol propyl alcohol butyl alcohol

CH3 CH3 CH3

CH3 CH OH CH3 CH CH2 OH CH3 C CH3

isopropyl alcohol isobutyl alcohol OH
(sec-propyl alcohol) tert - butyl alcohol
Alcohols and Ethers 13
 1
Give the common names of the following compounds.

a. CH3CH2CH2CH2 OH

b. CH3CH2 CH CH3
OH

c. OH
CH3 CH2 C CH3
CH3

d. CH2 CH CH2 OH

a. Since the alkyl group (C4H9 ) to which OH is attached has a straight

chain structure , the compound is called n–butyl alcohol.

b. Since the carbon atom with the OH group is attached to two other car-
bons, the compound is a secondary alcohol. The alkyl group (C4H9 ) is
butyl, so the name of the compound is sec-butyl alcohol.

c. Since the carbon atom that has the OH group is bonded to three alkyl
groups, the compound is a tertiary alcohol. The alkyl group (C5H11 ) is
pentyl then the compound is named as tert-pentyl alcohol.

d. The unsaturated hydrocarbon derivative attached to the OH group is

called propenyl, therefore the alcohol name is propenyl alcohol.

2.2. USING THE IUPAC SYSTEM

The following procedure should be followed to name alcohols according to the
IUPAC system.

1. Select the longest continuous carbon chain to which the hydroxyl group is
attached. Change the name of the alkane corresponding to this chain by drop-
ping the final –e and adding the suffix – ol.

2. Number the carbon atoms in the longest continuous carbon chain starting
from the end nearest to the hydroxyl group. The carbon atom bearing the
hydroxyl group takes the lower number. Indicate the position of the hydroxyl

14 Oxygen And Nitrogen Containing Organic Compounds

group by using this number; indicate the position of other substituents (as pre-
fixes) by using the numbers corresponding to their positions along the carbon
chain.

3 2 1 3 2 1 4 3 2 1
CH3 CH2 CH2 OH CH3 CH CH2 CH3 CH CH CH3

OH Cl CH3 OH
1 – propanol 1 – chloro – 2 – propanol 3 – methyl – 2 – butanol
n – propanol

For straight chained compounds, if the OH is attached to the first carbon,

instead of number “1”, the letter “n”, meaning normal, can be used.

If the OH group is attached to an unsaturated hydrocarbon chain, the num-

ber of the carbon bearing the OH group is substituted between the name of
hydrocarbon and the suffix –ol. If the OH group is attached to the first carbon
of the unsaturated hydrocarbon chain, the number of the carbon bearing the
OH group is not written.

3 2 1 3 2 1 1 2 3 4 5
CH2 CH CH2 OH CH C CH2 OH CH3 CH CH2 CH CH2
OH
2 – propenol 2 – propynol 4 – pentene – 2 – ol

If the OH group is in the middle of the chain, the numbering of the carbon
atoms starts at the end nearest any branching.

5 4 3 2 1
CH3 CH2 CH CH CH3 CH2 CH CH3

OH Br OH
2 – bromo – 3 – pentanol 1 – cyclohexyl – 2 – propanol

If there are more than one OH group, “di, tri, tetra....” are used before the suf-
fix –ol.

The numbers of the carbon atoms bearing OH groups are written before the
name of the alcohol.

CH2 CH2 CH2 CH2 CH2 CH2 CH CH2

OH OH OH OH OH OH OH
1, 2 – ethanediol 1, 3 – propanediol 1, 2, 3 – propanetriol
Ethylene glycol Trimethylene glycol Glycerol

Alcohols and Ethers 15

 2
Give IUPAC names for the following compounds.
a. CH3 CH CH2 CH3

OH

b. CH3 CH2 CH CH CH2

OH

c. OH

Br

d. CH CH2 OH

CH3

a. The chain has four carbons and the OH group is attached to the second
so it is named 2–butanol (sec–butyl alcohol).

b. The OH group is in the middle of the chain and the hydrocarbon chain is
unsaturated. Numbering is started at the end nearer to the double bond. The
chain has 5 carbons so the parent name is pentene.

The double bond is between first and second carbon atoms and the OH
group is attached to the third carbon atom. So the name of the compound
is 1-penten-3-ol.

c. The OH group is attached to a cyclohexane. Numbering starts from the

carbon atom bearing the OH group so that the carbon bearing bromine
is given the lower number. The name of compound is 3–bromocyclohexa-
nol.

d. The longest aliphatic carbon chain has 3 carbons. Numbering starts at the
end nearest the OH group. OH is attached to the first carbon and the
phenyl group is attached to the second carbon atom.
2 1
CH CH2 OH
3
CH3

16 Oxygen And Nitrogen Containing Organic Compounds

 3
Draw the structural formulae of the following compounds.
a. 1–methylcyclohexanol
b. 2,3–dimethyl–2,3–butanediol
c. 2,4–dimethyl–1–pentanol
d. 4–phenyl–2–pentanol

a. To a cyclohexane molecule a methyl and a hydroxyl group are attached.

The structure is CH3
OH

b. Two methyl and two hydroxyl groups are bonded to a hydrocarbon chain with
four carbons. Both the 2nd and 3rd carbon atoms have one methyl and one
hydroxyl group attached.

The structure is CH3 OH

CH3 C C CH3

OH CH3

c. Two methyl and one hydroxyl group are attached to a hydrocarbon chain con-
taining 5 carbons. The 1st carbon atom bears the hydroxyl group, the 2nd and
4th carbons bear the CH3 groups.

The structure is CH3 CH CH2 CH CH2 OH

CH3 CH3

d. A hydrocarbon containing 5 carbon atoms has one hydroxyl group on the

second carbon and a phenyl group on the fourth carbon.

The structure is CH3 CH CH2 CH CH3

C6H5 OH

3. PHYSICAL PROPERTIES OF ALCOHOLS

Alcohol molecules are formed by nonpolar alkyl (R ) and polar hydroxyl ( OH)
groups. These two groups play an important part in determining the physical prop-
erties of alcohols.

Alcohols and Ethers 17

 The physical properties of alcohols lay somewhere between the physical proper-
ties of hydrocarbons and water depending upon the R and OH groups that
make up the alcohol molecule. The hydrocarbon properties become more sig-
nificant as the number of carbon atoms in the molecule increases. Similarities to
water become more obvious in smaller molecules.

For example, in methanol, the hydroxyl group has a strong influence. Methanol
and water are miscible in all proportions. Methanol is polar and similar to water.

a. b.
+
H d H d
+
H d
+
–
d – –
O O d d O
R H H
+ +
R d d
H +
O d +
d H H d+
– O
d –
d
+ +
H d d H
–
d
O –
O H d+
d
R

a. Hydrogen bonding in alcohol molecules

b. Hydrogen bonding in water molecules

The polarity of alcohols decreases as the length of the hydrocarbon chain in the
molecule increases. Consequently, their solubilities in water decrease. At room
temperature, the solubilities of n-butanol, n-pentanol and n-octanol in 100 ml of
water are 8.3 g, 2.4 g and 0.05 g respectively.

Branching of alcohols increases solubility. For example, the solubility of n-butyl

alcohol is 8.3 g per 100 ml of H2O but tert-butyl alcohol is completely soluble in
water.

The polarity of alcohols increases as the number of OH groups increases.

Ethylene glycol, C2H4(OH)2 and glycerol, C3H5(OH)3 are soluble in water in any
proportion. Also, longer chained alcohols such as 1,4-butandiol, 2,3-butandiol
and the three isomers of pentandiol are highly soluble in water.

The boiling points of alcohols are much higher than that of their corresponding
hydrocarbons since alcohol molecules are polar and undergo hydrogen bonding.
For example, methane has a boiling point of –162°C while methanol has a boil-
ing point of 64.7°C.

18 Oxygen And Nitrogen Containing Organic Compounds

a. CH3 b. H
O O O
CH3 H H H H H H
H O
O O O H O
H H H H O H
H
O H
CH3 H CH4
H
O

CH3 O H
H

a. Like most alcohols, methyl alcohol is polar. Therefore, it is highly soluble in

water which is a good polar solvent.
b. Like many organic compounds, methane has a nonpolar structure and
therefore it is not soluble in water.

The boiling points of alcohols increase with increasing molar mass as van der
Waals forces increase with increasing molecular size. At the same time as the
boiling point increases volatility decreases. In primary alcohols, increasing the
branching in alkyl groups decreases the boiling point. When alcohols branch, the
surface contact of molecules decreases and therefore the van der Waals forces
decrease.

The boiling points of three isomers of primary pentanol are shown below.

CH3 CH2 CH2 CH2 CH2 OH

1 – pentanol
(n – pentanol)
boiling point : 138 °C
boiling point (°C)

CH3 250

CH3 CH CH2 CH2 OH 200

150
3 – methyl 1 – butanol
(isopentanol) 100
boiling point : 132 °C
50

CH3
1 2 3 4 5 6 7 8 9 10 11
CH3 C CH2 OH number of C atoms in the straight chain

CH3 Figure1 : Number of carbon atoms in straight chain

alcohols versus boiling point
2, 3 – dimethyl propanol
(neopentanol)
boiling point : 113 °C

Alcohols and Ethers 19

 Melting Boiling Density Solubility
Alcohol Formula
Point (°C) Point (°C) (g/mol) (g/100 mL water)
Methyl alcohol CH3OH – 97 64.7 0.792 f
Ethyl alcohol C2H5OH – 117 78.3 0.789 f
n – propyl alcohol CH3CH2CH2OH – 126 97.2 0.804 f
Isopropyl alcohol (CH3)2CHOH – 88 82.3 0.786 f
n – butyl alcohol CH3(CH2)3OH – 90 117.7 0.810 
Isobutyl alcohol (CH3)2CHCH2OH – 108 108.0 0.802 10
sec – butyl alcohol CH3CH2CHOHCH3 – 114 99.5 0.808 26
tert – butyl alcohol (CH3)3COH 25 82.5 0.789 f
n – pentyl alcohol CH3(CH2)4OH – 78,5 138 0.817 2.30
n – hexyl alcohol CH3(CH2)5OH – 52 156.5 0.819 0.60
n – heptyl alcohol CH3(CH2)6OH – 34 176 0.822 0.20
n – octyl alcohol CH3(CH2)7OH – 15 195 0.825 0.05
n – nonyl alcohol CH3(CH2)8OH – 5.5 212 0.827 –
n – decyl alcohol CH3(CH2)9OH 6 228 0.829 –

Cyclohexyl alcohol OH 24 161.5 0.962 3.60

Benzyl alcohol C6H5CH2OH – 15 205 1.046 4

Ethylene glycol HO(CH2)2OH – 12.6 197 1.113 f
Propylene glycol HO(CH2)3OH – 59 187 1.040 f
Glycerol C3H5(OH)3 18 290 1.261 f
Allyl alcohol CH2 CHCH2OH – 129 97 0.855 f

Table 1: Physical properties of some alcohols

In a monoalcohol, from the primary to tertiary structure, the boiling point

decreases since the branching increases. The boiling points of primary, second-
ary and tertiary butanols are given below;

CH3 CH3

CH3 CH2CH2CH2 OH CH3CH2 CH OH CH3 C OH

CH3
n – butyl alcohol sec - butanol tert - butanol
boiling point boiling point boiling point
117.7 °C 99.5°C 82.5°C

20 Oxygen And Nitrogen Containing Organic Compounds

The melting point of alcohols increase as the number of carbon atoms increase.
At room temperature the normal alcohols (C1 C11) up to dodecanol
(C12H25OH, m.p. = 24°C) are liquids and the others with carbon numbers
greater than 11 are all solids. Branching generally decreases the melting points
of alcohols (compare the melting points of n–butyl alcohol and iso–butyl alcohol)
although symmetric branching leads to an increase in melting point.
CH3 CH3

CH3CH2CH2CH2 OH CH3 CH CH2 OH CH3 C OH

CH3
n – butyl alcohol isobutyl alcohol tert - butyl alcohol
melting point : – 90 °C melting point : – 108 °C melting point : 25 °C

4
Arrange the following compounds in order of decreasing solubility in water.
I. CH3 CH2 CH2 CH3
II. CH3 (CH2)3 CH2 OH
III. CH3 CH CH2 CH2

OH CH3
IV. HO CH2 (CH2)3 CH2 OH

The first molecule is an alkane, the others are alcohols. Alkanes are not soluble
in water. As a result, the compound CH3CH2CH2CH3 is the least soluble.
Since the fourth compound has two OH groups, it is more soluble than the
others.
Consequently, the order of decreasing solubilities of given compounds in water
is: IV > III > II > I

5
Arrange the following compounds in order of decreasing boiling points.
I. C2H5OH II. C3H7OH III. CH CH2 IV. H
2

OH OH CH3 C OH

CH3

Alcohols and Ethers 21

 All the compounds are alcohols. It is known that when the molar mass of alco-
hols increases the boiling point also increases. The first compound, C2H5OH (46
g/mol) therefore has the lowest boiling point. The second and fourth compounds
are isomers of propanol. As the number of branches increases, the boiling point
decreases. The fourth alcohol has more branches than the second one, so it has
a lower boiling point. The molar mass of ethylene glycol (3rd compound) is near
to that of propanol. However since it has two –OH groups, it boils at a higher
temperature.
As a result the boiling point order is III > II > IV > I.

4. CHEMICAL PROPERTIES OF ALCOHOLS

The chemical properties of alcohols are determined by the oxygen atom in the
2.5
d–
O O OH group. This oxygen atom is bonded to a carbon and hydrogen atom by
+
C d H d+ C H 2.1 sigma (single) bonds. The bonds between C O and O H are polar. The elec-
tronegativities of oxygen, carbon and hydrogen are 3.5, 2.5 and 2.1 respective-
3.5 ly, oxygen having the highest electronegativity.
polar covalent
bonds
When the polarities of C O and O H bonds are compared, it is seen that the
Because of the difference in electroneg- O H bond is more polar than the C O bond. The hydrogen atom in the
ativities between C , O and H alcohols
have polar properties. O H bond becomes partially positively charged and therefore in some reac-
tions, alcohols can act as proton (H+) donors. From primary alcohols to tertiary
alcohols the polarity and therefore the proton donating ability of the O H
bond decreases.

4.1. REACTIONS OF ALCOHOL INVOLVING O — H BOND

BREAKAGE
Pure alcohols can undergo self-ionization in the same way as water but the ion-
ization of pure alcohols is less than that of water. During the ionization, an alco-
hol molecule is converted into an alkoxide (RO–) ion by when it loses a proton,
the molecule accepting the proton is converted into an oxonium ion.

+
R O H + R O H R O H + R O
H
alcohol alcohol oxonium alkoxide
ion ion

CH3OH + CH3OH CH3O+H2 + CH3O– Ka= 3.16 · 10-16

methanol methanol methoxide

22 Oxygen And Nitrogen Containing Organic Compounds

 C2H5OH + C2H5OH C2H5O+H2 + C2H5O– Ka= 1.26 · 10-16
ethanol ethanol ethoxide

The ionization percentage of alcohols decreases as the number of carbon atoms

increases. In reactions with alcohols involving O H bond breakage, protons
(H+) are donated.

Reactions of Alcohols with Alkali Metals

Alcohols display the properties of weak acids. The reactions of alcohols with
active metals (such as Na and K) are slower than the equivalent reactions with Potassium reacts with water and pro-
water. During these reactions, basic salts of the alkoxide ion (RO ) are pro- duces potassium hydroxide and hydro-
duced. gen.

slow – +
R O H + Na R O Na +1/2H2
alcohol sodium alkoxide

fast – +
H O H + Na H O Na + 1/2H2
water sodium hydroxide

Methanol and ethanol react strongly with Na and K. When the carbon chain of
the alcohol extends the intensity of the reaction decreases. Generally, potassium
is preferred for the long-chained alcohol reactions. Some metals, such as mag-
nesium and aluminum can react with alcohols to produce H2 gas when their
oxide layers are cleaned from their surfaces.

2CH3CH2OH + 2Na 2CH3CH2ONa + H2 Ethanol reacts with sodium and produces

sodium ethoxide sodium ethoxide and hydrogen. When
sodium is put into ethanol, it settles down
– +
CH2 OH CH2 O Na and reacts slowly.
– +
CH OH + 3Na CH O Na + 3/2H2
– +
CH2 OH CH2 O Na
glycerol sodium glycerate
H2O
Activity decreases

The rate of reaction of alcohols with alkali metals decreases from primary alco- CH3OH
hols to tertiary alcohols. Basic alkoxides react with water (hydrolyze) to produce
their initial alcohols. CH3CH2OH

R O–Na+ + H OH R OH + NaOH CH3CH2CH2OH

alkoxide water alcohol

C3H7 O–Na+ + H OH C3H7 OH + NaOH The activity order of some

sodium propylate water propyl alcohol molecules (containing the
–OH group) with Na and K
metals

Alcohols and Ethers 23

 6
40 grams of 92% pure (by mass) ethyl alcohol reacts with an excess amount of
potassium metal. How many liters of H2 gas are produced at the end of the reac-
tion at STP (impurities in the mixture do not react with potassium).
(C2H5OH : 46 g/mol)

Let’s calculate the number of moles of ethyl alcohol. Firstly the mass of pure
ethyl alcohol is calculated.
92
mC2H5OH = 40 g · ––––– = 36.8 g
100
The number of moles of ethyl alcohol is found.
m 36.8 g
nC2H5OH = ––––– = ––––––––––– = 0.8 mol
M 46 g/mol
The reaction between ethyl alcohol and potassium is
2C2H5OH + 2K o 2C2H5OK + H2n
We can find the mole number of hydrogen from the mole number of the alcohol
by proportion:
2 mol C2H5OH 1 mol H2
0.8 mol x
——————————————————
nH = x = 0.4 mol
2

So the volume of hydrogen at STP is:

VH2 = 0.4 · 22.4 = 8.96 L.

7
When 20 grams of an ethane - ethanol mixture is reacted with an excess amount
of Na metal, 2.8 L of H2 gas is produced at STP. What was the mass percentage
of ethyl alcohol in the original mixture?
(C2H5OH : 46 g/mol)

The collection of H2 gas over water pro-
duced from the reaction of ethanol with
sodium can easily be observed.
Since ethane is a paraffin, it does not react with sodium. The reaction of ethyl
alcohol with sodium is
2C2H5OH + 2Na o 2C2H5ONa + H2

24 Oxygen And Nitrogen Containing Organic Compounds

The mole number of hydrogen produced is:
2.8 L
nH2 = ––––––––––––– = 0.125 mol
22.4 L/mol
The mole number of ethanol is twice the mole number of hydrogen so:
nC = 2 . nH = 2 . 0.125 = 0.25 mol
2H5OH 2

Then the mass of ethanol is

mC2H5OH = n . M Ÿ 0.25 mol . 46 g/mol = 11.5 g
Since the mixture is 20 grams, the percentage of alcohol is
Ethyl alcohol % = (11.5 g / 20 g) . 100 = 57.5

Esterification Reactions
From the reaction between alcohols and carboxylic acids, esters and water are
produced. This is called esterification. In this reaction, the hydrogen atom from
the OH group of an alcohol is replaced by the acyl group from a carboxylic
acid. These reactions occur in the presence of strong acid catalysts such as HCl
or H2SO4.

+
H
R C O + R¢ O H R C O + H O H

O H O R¢
carboxylic acid alcohol ester water

+
H
CH3 C O + C2H5 O H CH3 C O + H O H

O H O C2H5
acetic acid ethyl alcohol ethyl acetate water

Inorganic acids also react with alcohols to form esters. In these esterification
reactions, as well as HNO3, H2SO4 and H3PO4 , inorganic acid halides such as
SOCl2, and PCl3 can be used.

HONO2 + R OH R O NO2 + H2O

nitric acid alcohol ester water

CH2 OH CH2 O NO2

CH OH + 3HONO2 CH O NO2 + 3H2O

CH2 OH CH2 O NO2

glycerol trinitroglycerol

Alcohols and Ethers 25

 8
1 mole of acetic acid (CH3COOH) reacts with 1 mole of a monohydric alcohol to
produce an ester with a molar mass of 102 g/mol. What is the molecular formu-
la of the alcohol used in the reaction?
CH3COOH : 60 g/mol, H2O : 18 g/mol
H : 1 g/mol
C : 12 g/mol
O : 16 g/mol

In esterification reactions, 1 mol of carboxylic acid reacts with 1 mol of monohy-

dric alcohol to produce 1 mol of ester and 1 mol water.

Carboxylic acid + Monohydric alcohol o Ester + Water.

Since total mass is conserved in a chemical reaction, the sum of the mass of
alcohol and acid should be equal to sum of the mass of ester and water.

macid + malcohol = mester + mwater

60 + malcohol = 102 + 18

malcohol = 60 gram

So 1 mol of monohydric alcohol is 60 gram. Since the general formula of mono-

hydric alcohols is CnH2n+1OH, the following calculation can be done.

MC = 60 g/mole
nH2n+1OH

12n + (2n + 1) . 1 + 16 + 1 = 60
14n = 42
n=3
We can write the molecular formula as C3H7OH, propyl alcohol.

9
When a 115 gram sample of impure ethyl alcohol (C2H5OH) is reacted with an
excess amount of acetic acid (CH3COOH), 176 grams of ester is obtained. What
is the mass percentage of pure alcohol in the sample?
(C2H5OH : 46 g/mol, CH3COOH : 60 g/mol)

26 Oxygen And Nitrogen Containing Organic Compounds

The esterification reaction of ethyl alcohol:
O O
H2SO4
C2H5OH + HO C CH3 C2H5O C CH3 + H2O
ethyl alcohol acetic acid ethyl acetate

The molar mass of the ester:

MC = (4 . 12) + (8 . 1) + (2 . 16) = 88 g/mol
4H8O2
The number of moles of ester
m 176 g
nC H O = ––––– = –––––––––––– = 2 mol
4 8 2 M 88 g/mol
According to the reaction, the number of moles of alcohol is equal to the num-
ber of moles of ester;

nC = nC = 2 mol
2H5OH 4H8O2

Then the mass of the alcohol is

mC = M . n = 46 g/mol . 2 mol = 92 g
2H5OH

Finally we can find the mass percentage of pure alcohol in the sample.

in 115 g sample 92 g is ethyl alcohol

in 100 g sample xg
—————————————————————————————
92 . 100
x = ————— = 80%
115

4.2. REACTIONS OF ALCOHOLS INVOLVING C — O BOND

BREAKAGE
In alcohols it is seen that the R C O structure has two pairs of nonbonded
electrons.
H

These electrons cause alcohols to be protonated (accept protons) in acid solu-

tions. In these type of reactions alcohols act as base.

+
During the reaction the oxonium ion R C O H is produced.

If this ion encounters a strong electrophile (a species attracted to electrons), a

water molecule is removed from the ion as a result of C O bond breakage.

Alcohols and Ethers 27

 +
Electrophilic atoms or atom groups bond to carbon in the R C structure.

These type of reactions are explained below.

Reactions of Alcohols with Hydrogen Halides

Alcohols react with hydrogen halides to produce alkyl halides. In these reactions,
the OH group of the alcohol is replaced by the halide ion of the acid. All alco-
Activity order of HX : HI > HBr > HCI
hols react with concentrated HBr and HI solutions to produce alkyl bromide and
alkyl iodide. These reactions occur by a specific mechanism as shown below.

ROH + HX o RX + H2O (X : Br, I)

C2H5OH + HI o C2H5I + H2O

Concentrated HCl solution reacts with tertiary alcohols directly but only reacts
with primary and secondary alcohols in the presence of a ZnCl2 catalyst. A solu-
tion of ZnCl2 salt in HCl is known as “Lucas reagent”.

ZnCl2
R CH2 OH + HCl o R CH2 Cl + H2O
25°
(CH3)3C OH + HCl o (CH3)3C Cl + H2O
ZnCl2
(CH3)2CH OH + HCl o (CH3)2CH Cl + H2O
ZnCl2
CH3 CH2 OH + HCl o CH3 CH2 Cl + H2O
heat

The Reactions of Alcohols with Acid Halides

+ + –
R O +H R O H+ X R X + O H
H H H
The reactions of alcohols with acid halides occur in two steps. In the first step, lone
pairs of electrons on the oxygen atoms in alcohol molecules attract proton (H+)
from the acid to form the oxonium ion.

In the second step, the bond between the alkyl group (R–) and oxygen atom weak-
ens and is then broken. Oxygen takes the bonding electrons, thus the R– group
becomes positively charged. The negatively charged ion of the acid halide bonds to
the positively charged alkyl group (R+–) to form the R – X compound.

28 Oxygen And Nitrogen Containing Organic Compounds

 10
Write the equations for the reactions between the following substances.
a. 2–propanol + Lucas reagent
b. 2–methyl–2–butanol + HCl

a. Since 2–propanol compound is a secondary alcohol, it reacts with Lucas

reagent to form isopropyl chloride.
ZnCl2
CH3 CH CH3 + HCl CH3 CH CH3 + H2O

OH Cl
2–propanol isopropyl chloride

b. 2–methyl–2–butanol is a tertiary alcohol. Therefore it reacts with HCl at 25°C

readily. In the reaction, the OH group of the second carbon of the alcohol
is replaced by the Cl atom from HCl and tert-butyl chloride is formed.
CH3 CH3
25 °C
CH3 C OH + HCI CH3 C Cl + H2O

C2H5 C2H5
2–methyl–2–butanol tert - butyl chloride
(tert-pentanol)

Dehydration of Alcohols
1. When one mole of monohydric alcohol is heated in the presence of a concen-
trated H2SO4 catalyst at high temperature, one mole of water and one mole of
alkene is produced. To undergo this reaction, the carbon adjacent to the car-
bon with the OH group needs a H atom bonded to it.
H2SO4
R CH2 CH2 OH o R CH CH2 + H2O
180 °C
H2SO4
CH3 CH2 CH2 OH o CH3 CH CH2 + H2O
180 °C

The reaction follows Markovnikov’s rule.

2. At a lower temperature, a simple ether can be produced from the dehydra-

tion of two moles of monohydric alcohols.
H2SO4
R OH + HO R R O R + H2O
140 °C
alcohol alcohol ether water

Alcohols and Ethers 29

 H2SO4
CH3 OH + HO CH3 CH3 O CH3 + H2O
140 °C
methyl methyl dimethyl ether water
alcohol alcohol

R O R¢
H2SO4
R OH + R¢ OH R O R + H2O
140 °C

R¢ O R¢

1 mol 1 mol 1 mol 1 mol

mixture of ethers

11
Write the equations for the following reactions.
a. Dehydration of n – butanol in the presence of a H2SO4 catalyst at 180 °C.
b. Dehydration of isopropanol in the presence of a H2SO4 catalyst at 140 °C.

a. When 1 mol of n-butanol is heated up to 180 °C, an alkene and 1 mol water
are produced.
H2SO4
CH3 CH2 CH2 CH2 OH o CH3 CH2 CH CH2 + H2O
180°C
n–butanol n–butene

b. 2 mol isopropanol can produce 1 mol water when heated up to 140 °C in the
presence of a H2SO4 catalyst. In this reaction the OH group of an alcohol
and the H from the OH group of other alcohol join together to form water.
The remaining alcohol fragments bond to each other. As a result, isopropyl
ether is formed.

CH3 CH3 CH3 CH3

CH3 CH OH + HO CH CH3 CH3 CH O CH CH3 + H2O

isopropanol isopropanol di–isopropyl ether

12
A sample of 50 gram of 92% pure ethyl alcohol is used to produce ethylene with
an 80% yield,
a. How many grams of alkene can be obtained?
b. How many grams of ether can be obtained?
(C2H5OH : 46 g/mol, C4H10O : 74 g/mol)

30 Oxygen And Nitrogen Containing Organic Compounds

 92
a. The amount of pure alcohol is 50 g . ——— = 46 g
100
46 g
the number of moles of ethyl alcohol is; n = ————— = 1 mol.
46 g/mol
From the dehydration of 1 mol ethyl alcohol, 1 mol ethylene is obtained.
H2SO4
C2H5OH o C2H4 + H2O
180 °C
1 mol 1 mol 1 mol

The molar mass of ethylene is = 2 . 12 + 4 . 1 = 28 g/mol. mC2H4 = 28 g

But the reaction has an 80% yield. So the mass of ethylene produced is
80
mC2H4 = 28 . ——— = 22.4 g
100

b. As can be seen in the given equation, at 140 °C with the help of H2SO4 , from
the dehydration of 2 moles of ethyl alcohol 1 mole of ether is obtained.
2C2H5OH o C2H5 O C2H5 + H2O
If 1 mole C2H5OH is used at the beginning of the reaction,
2 mol of alcohol 1 mol of ether
1 mol of alcohol x mol of ether
————————————————————
x = 0.5 mol of ether is obtained at the end.
Then the mass of ether is calculated.
m m
n = —— 0.5 = —— m = 37 g
M 74
But the reaction has only an 80% yield. So the mass of ether produced is;
80
MC4H10O = 37 . ——— = 29.6 g ether
100

4.3. OXIDATION OF ALCOHOLS

To oxidise alcohols, acidic solutions of strong oxidising agents, such as KMnO4,
K2Cr2O7 or K2CrO4 are used.
The degree of oxidation of alcohols depends on the number of H atoms bonded
to the carbon atom bearing the OH group.
H H R¢¢

R C OH R C OH R C OH

H R¢ R¢
Primary alcohols Secondary alcohols Tertiary alcohols
can be oxidized by two degrees can be oxidized by one degree cannot be oxidized

Alcohols and Ethers 31

 Oxidation of Primary Alcohols
In primary alcohols, the carbon atom bearing the OH group has two hydro-
gen atoms, except methanol, which has three.

Therefore, primary alcohols can be oxidised two degrees. In the first oxidation,
an aldehyde is produced, in the second oxidation, a carboxylic acid is produced.

The notation [O] above the arrows in O O

[O] [O]
the reaction equations indicates oxida- R CH2 OH R C R C
– H2O
tion by the addition of oxygen from an
H OH
oxidant. primary alcohol aldehyde carboxylic acid

Let’s examine the oxidation of ethyl alcohol.

O
[O]
1st degree CH3 CH2 OH – H 2O
CH3 C
H
ethyl alcohol acetaldehyde

O O
[O]
2nd degree CH3 C CH3 C
H OH
acetaldehyde acetic acid

Oxidation of Secondary Alcohols

In secondary alcohols, there is only one hydrogen atom on the carbon atom
bearing the OH group. Therefore, secondary alcohols can be oxidised by only
one degree. The end product of the oxidation is a ketone.
R R
[O]
R C OH – H2O
C O

H R¢
secondary alcohol ketone

CH3 H3C
[O]
H3 C C OH – H2O
C O

H H3C
secondary propanol acetone

Oxidation of Tertiary Alcohols

Tertiary alcohols can not be oxidised because they do not have a hydrogen atom
on the carbon atom bearing the OH group.

32 Oxygen And Nitrogen Containing Organic Compounds

 R
[O]
R C OH no reaction

R
tertiary alcohol

However, if tertiary alcohols are heated up to very high temperatures in the pres-
ence of a catalyst, they can decompose into unsaturated hydrocarbons and
water.

13
Write out the following reactions.
a. Oxidation of methanol by K2Cr2O7 in H2SO4 solution.
b. Oxidation of 2-propanol by KMnO4 in H2SO4 solution.

a. Oxidation of methanol (CH3OH) occurs in three steps, as methanol has 3 H

atoms directly bonded to C atom.
In the first step, methanol oxidises to an aldehyde (methanal).

3CH3OH + K2Cr2O7 + 4H2SO4 o 3HCHO + K2SO4 + Cr2(SO4)3 + 7H2O

In the second step, the formed aldehyde oxidises to carboxylic acid (methanoic
acid)
3HCHO + K2Cr2O7 + 4H2SO4 o 3HCOOH + K2SO4 + Cr2(SO4)3 + 4H2O
In the third step oxidation produces carbonic acid from carboxylic acid which
is unstable and decomposes to CO2 and H2O.
3HCOOH + K2Cr2O7 + 4H2SO4 o 3H2CO3 + K2SO4 + Cr2(SO4)3 + 4H2O
H2CO3
CO2n + H2O

b. 2–propanol is a secondary alcohol. So it is fully oxidised in only one step. The

product will be a ketone (2–propanone)

5CH3 CH CH3 + 2KMnO4 + 3H2SO4

OH
O

5CH3 C CH3 + K2SO4 + 2MnSO4 + 8H2O

Alcohols and Ethers 33

 14
The molar mass of an aldehyde which is produced by the one degree oxidation
of a monohydric alcohol is 46 g/mol. Calculate the molar mass of the alcohol
used in this reaction.

[O]
R CH2 OH R C O + H2O

x g/mol H
(x – 2) g/mol

According to the reaction, 1 mol of an alcohol can produce 1 mol of an aldehyde.

Two hydrogen atoms from the alcohol are used in the formation of water. Therefore
the molar mass of the aldehyde produced is 2 g/mol less than that of the alcohol.
Molar mass of aldehyde = x – 2 = 46 g/mol
Molar mass of alcohol, x = 48 g/mol

15
A 10 grams mixture of 2 - methyl - 2 - propanol and 2 - butanol is reacted with
excess K2Cr2O7 in acidic solution. At the end of the reaction 3.6 grams of ketone
is obtained. Find the percentage of 2 – butanol in the original mixture.

2 - methyl - 2 - propanol is a tertiary alcohol; 2 - butanol is a secondary alcohol.

Secondary alcohols are oxidised to ketones but tertiary alcohols do not undergo
oxidation.
CH3

CH3 C OH + K2Cr2O7 + H2SO4 no reaction

CH3

3CH3 CH CH2 CH3 + K2Cr2O7 + 4H2SO4

OH
3CH3 C CH2 CH3 + K2SO4 + Cr2(SO4)3 + 7H2O

34 Oxygen And Nitrogen Containing Organic Compounds

A ketone (methyl ethyl ketone) is produced by the oxidation of 2 - butanol. The
molar mass of the ketone is:
MC = (4 . C) + (8 . H) + O
4H8O

MC = (4 . 12) + (8 . 1) + 16 = 72 g/mol
4H8O

m 3.6 g
n = —— = ————— = 0.05 mol
M 72 g/mol
According to the balanced equation given above,
3 mol of butanol produces 3 mol of methyl ethyl ketone
x mol of butanol produces 0.05 mol of methyl ethyl ketone
——————————————————————————————
x = 0.05 mol
M of 2 - butanol is MC = (4 . C) + (10 . H) + (1 . O) = 74 g/mol
4H10O

mC = n . M = 0.05 . 74 = 3.7 gram

4H10O

10 g mixture has 3.7 g of 2 - butanol

100 g mixture has xg
————————————————————————
x = 37 g
the percentage of 2 - butanol is 37% in the original mixture.

4.4. COMBUSTION REACTIONS OF ALCOHOLS

Alcohols, like hydrocarbons, burn in excess oxygen to form CO2 and H2O.
Combustion reactions of monohydric, dihydric and trihydric alcohols are given
below.

Monohydric alcohol:
3n
CnH2n+1 (OH) + —— O2 o n CO2 + (n + 1)H2O
2
C3H7OH + 9/2O2 o 3 CO2 + 4H2O

Dihydric alcohol:
3n – 1
CnH2n (OH)2 + ——— O2 o nCO2 + (n + 1)H2O
2
C2H4(OH)2 + 5/2O2 o 2CO2 + 3H2O

Trihydric alcohol:
3n – 2
CnH2n – 1 (OH)3 + ——— O2 o nCO2 + (n + 1)H2O
2
C4H7(OH)3 + 5O2 o 4CO2 + 5H2O

Alcohols and Ethers 35

 16
When 0.25 mol of a monohydric alcohol is burned, 16.8 L of CO2 gas is pro-
duced at STP.
What is the molecular formula of the alcohol?

Combustion of monohydric alcohols:

3n
CnH2n+1OH + ——— O2 o nCO2 + (n+1)H2O
2

16.8 L
nCO = ——————— = 0.75 mol
2
22.4 L/mol

If 0.25 mol of alcohol is burned 0.75 of mol CO2 is produced

If 1 mol of alcohol is burned n mol of CO2 is produced
—————————————————————————————————
n = 3 mol

If we substitute n = 3 into the general formula, CnH2n+1OH; the molecular for-

mula will be C3H7OH.

5. PREPARATION OF ALCOHOLS
5.1. SYNTHESIS OF ALCOHOLS FROM ALKENES
Alcohols can be prepared by the acid catalysed addition of water to alkenes.
Concentrated H2SO4 is used as catalyst. The addition follows Markovnikov’s rule.
Secondary and tertiary alcohols can be produced by this method, but primary
alcohols cannot (except for ethanol).
H2SO4
R CH CH2 + H OH R CH CH2
alkene water OH H
secondary alcohol

H2SO4
CH3 CH CH2 + H OH CH3 CH CH3

propene water OH
secondary propanol

This reaction is reversible and the mechanism for the hydration of an alkene is
simply the reverse of that of the dehydration of an alcohol.

36 Oxygen And Nitrogen Containing Organic Compounds

5.2. SYNTHESIS OF ALCOHOLS FROM ALKYL HALIDES
Hydration of alkyl halides by alkaline hydroxides produces alcohols. In this reac- Alkaline hydroxides are bases that are
tion the halogen atom is replaced by the OH group to form an alcohol. soluble in water. Hydroxides of all group
1A metals and calcium, strontium and
R X + NaOH o R OH + NaX
alkyl halide alkaline hydroxide alcohol alkaline halide barium from group 2A are alkaline.

CH3CH2 CI + NaOH o CH3CH2 OH + NaCl

ethyl chloride sodium ethyl alcohol sodium
hydroxide chloride

5.3. SYNTHESIS OF ALCOHOLS BY THE REDUCTION OF

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS
Alcohols can be obtained by reacting of aldehydes, ketones or carboxylic acids
with hydrogen gas in the presence of a platinum (Pt) catalyst. As a result of the
reduction of aldehydes by one degree and carboxylic acids by two degrees pri-
mary alcohols are obtained. Reduction of ketones by one degree produces sec-
ondary alcohols.

Pt
ALDEHYDE PRIMARY ALCOHOL

O OH
Pt
R C + H2 R C H
H H

Pt
CARBOXYLIC ACID + 2H2 PRIMARY ALCOHOL
–H2O

O O OH
Pt Pt
R C + H2 R C + H2 R C H
–H2O
OH H H

Pt
KETONE + H2 SECONDARY ALCOHOL

O OH
Pt
R C + H2 R C H

R¢ R¢

5.4. SYNTHESIS OF ALCOHOLS USING GRIGNARD

REAGENTS
Grignard reagents, alkyl magnesium halides (R – Mg – X), react with aldehydes
and ketones.

Alcohols and Ethers 37

 The Grignard reagent reduces these compounds, which contain the
O

carbonyl group, ( C ) to alcohols.

I. If a primary alcohol is desired, the reaction should be initiated with formaldehyde.

By this way, an alcohol, containing at least two carbons, is produced.

H H
+HCI
C O + CH3 Mg Cl CH3 C O–Mg+CI CH3 CH2 OH
–MgCl2

H H
formaldehyde ethyl alcohol

II. If a secondary alcohol is desired, Grignard reagents should be reacted with

an aldehyde other than formaldehyde.

H CH3 CH3
– + +HBr
C O + CH3 MgBr H C O Mg Br CH3 CH OH
–MgBr2
H3C CH3
acetaldehyde isopropanol
sec – propanol

III. If a tertiary alcohol is desired the Grignard reagent should be reacted with a
ketone.

CH3 CH3 CH3

– + +HI
C O + CH3 MgI CH3 C O Mg I –MgI2
CH3 C OH
C2H5 C2H5 C2H5

2 – butanone tert - pentanol

17
Give the required reactants needed to produce the following compounds using
Grignard reagents and write down the chemical equations.
a. 1-butanol
b. 2-butanol
c. 2-methyl-2-propanol

38 Oxygen And Nitrogen Containing Organic Compounds

a. 1-butanol is a primary alcohol. To produce it, the reaction should be started
with formaldehyde and a Grignard reagent. Since formaldehyde has one car-
bon atom and butanol has four carbon atoms, the Grignard reagent should
have three carbon atoms.
H C3H7
– + + HCI
C O + C3H7 Mg Cl H C O Mg Cl – MgCI2 C3H7 CH2 OH
H H

b. 2-butanol is a secondary alcohol. To produce it, the Grignard reagent should

react with an aldehyde other than formaldehyde. Since the hydroxyl group is
attached to the second carbon of 2 - butanol, the aldehyde should have two
carbon atoms and the Grignard reagent should also have 2 carbon atoms.

H C2H5 C2H5
– + +HBr
C O + C2H5 Mg Br H C O Mg Br –MgBr2
CH3 CH OH
CH3 CH3

c. 2-methyl-2-propanol is a tertiary alcohol and contains 4 carbon atoms. To

produce it, a Grignard reagent should be treated with a ketone. The ketone
needs 3 carbons and the Grignard reagent needs 1 carbon so the total num-
ber of carbons will be equal to 4.

CH3 CH3 CH3

+HBr
C O + CH3 MgBr CH3 C O MgBr –MgBr2
CH3 C OH
CH3 CH3 CH3

6. SOME IMPORTANT ALCOHOLS

6.1. METHYL ALCOHOL (METHANOL)

Physical Properties
Methyl alcohol is colorless, flammable and has a characteristic odor. Its taste is
similar to ethanol but it is highly toxic. Ingestion of even small quantities of
methyl alcohol can cause blindness, large quantities cause death. Methyl alcohol
poisoning may also occur by inhalation of the vapors or by prolonged exposure
to the skin. Since methyl alcohol can be deadly, pyridin, which has a bad odor, To distinguish between ethanol and
methyl alcohol the borax test is used.
or dyes are added to it to prevent its use as a drink. As methyl alcohol has a low When boric acid reacts with methanol, a
freezing point (–97 °C), it has been used as antifreeze in radiators. pale green flame is observed.

Alcohols and Ethers 39

Addition of 5–30 % methyl alcohol to
gasoline decreases polluting particles
produced from car exhausts. Methyl
alcohol can be produced from sub-
stances other than petroleum. The most
important and the cheapest being coal.
It can also be produced from wood, agri-
cultural remnants and dumps.
However, its boiling point (64.7 °C) is lower than that of water, and so usage of
methyl alcohol has decreased in this area. Methyl alcohol can be dissolved in all
proportions in water and organic solvents and can also dissolve fats and resins.
Methyl alcohol can be converted into formaldehyde and this is the raw material
for industrial products such as plastics, paints and solvents.
Chemical Properties
Methyl alcohol is the most active and the most acidic member of the monohy-
dric alcohols.

CH3OH + H2O o CH3O– + H3O+

It displays all the properties of alcohols. It is easily flammable and burns with a
bluish flame.

Methyl alcohol can be easily oxidised. It turns into formaldehyde in the first degree
of oxidation, into formic acid in the second and carbon dioxide in the third.
[O] [O] [O]
CH3 OH o HCHO o HCOOH o H2CO3 o CO2 + H2O
–H2O –H2O
methyl alcohol formaldehyde formic acid carbonic acid carbon dioxide

In some countries, methyl alcohol is 18

used as fuel. Compared with gasoline,
methyl alcohol causes more wear to the Write the reactions of methyl alcohol with
engine, this is a disadvantage of methyl a. Sodium, b. Acetic acid, c. Acid halides
alcohol.

a. CH3OH + Na o CH3ONa + 1/2H2

b. CH3OH + CH3COOH o CH3COOCH3 + H2O

c. CH3OH + HX o CH3X + H2O

19
How many grams of formaldehyde must be used to produce 80 grams of methyl
alcohol in a reaction with a 75% yield? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

M of methyl alcohol:
M CH = 12 + (4 . 1) + 16 = 32 g/mol
3OH

40 Oxygen And Nitrogen Containing Organic Compounds

 m 80 g
n = ——— = —————— = 2.5 mol
M 32 g/mol
Reduction of formaldehyde by one degree produces methyl alcohol.
+H2
H C O CH3 OH

H
According to the equation 1 mole of methyl alcohol is produced by 1 mole of
formaldehyde. To produce 2.5 moles of methyl alcohol, 2.5 moles of formalde-
hyde must be used.
MHCHO = 12 + 2 + 16 = 30 g/mol
m = n . M = 2.5 . 30 = 75 g
The reaction occurs with a 75% yield.

for 75% yield 75 g formaldehyde is used

if 100% yield xg
———————————————————————————
x = 100 g

Synthesis
Methyl alcohol is the simplest member of the alcohols and is also known as methyl
alcohol or wood alcohol. It was originally produced from the distillation of wood at
high temperature in the absence of air, hence it is known as wood alcohol or wood
spirit. While heating, wood which is composed of cellulose, decomposes into sim-
pler compounds. Some of these compounds are acetone, acetic acid and methyl
alcohol. The mixture obtained is passed through cold water to condense it.

Up until 1925, this method was used to synthesize methyl alcohol. In 1920 how-
ever, methyl alcohol was produced more cheaply using a new method discovered
Germany. Here, methyl alcohol was produced by the more reaction of CO and
H2 gases under high pressure and temperature in the presence of a catalyst.
History
Today, most methyl alcohol is prepared by this method.
ZnO – Cr2O3 Ethyl alcohol has been known to
CO + 2H2 o CH3OH 'H = –90.5 kJ/mol humankind since prehistory as the
300 – 400°C/200 atm
active ingredient of alcoholic bever-
ages. Its isolation as a relatively pure
6.2. ETHYL ALCOHOL
compound was probably achieved first
Physical Properties by Islamic alchemists who developed
the art of distillation, such as Al–Geber
Pure ethyl alcohol is colorless and has a characteristic smell. It is miscible with
(721–815) and Al–Razi (864–930).
water and is toxic, affecting the central nervous system.

It freezes at –114 °C, boils at 78.3 °C and has a density of 0.789 g/mL

Alcohols and Ethers 41

 Chemical Properties
The ethyl alcohol that is used as a solvent in laboratories is composed of 95%
ethyl alcohol and 5% water. This mixture is called common ethyl alcohol. Such a
mixture is an example of an azeotropic mixture and boils at 78.15°C.

100% pure ethyl alcohol is known as absolute alcohol or absolute ethyl alcohol.
Pure ethyl alcohol can be prepared by adding lime (CaO) to common ethanol.
Using this method, H2O is precipitated as Ca(OH)2.

CaO + H2O o Ca(OH)2

Spirit is a derivative of ethyl alcohol, In industry, another method to prepare pure ethanol is to add benzene to the
used as fuel in cookers.
mixture of 95% ethanol and water. Benzene forms a different azeotrope with
ethanol and water. This azeotrope boils at 64.9°C and allows for the distillation of
pure ethanol.
To prevent the drinking
of ethyl alcohol, which Ethyl alcohol is an important organic solvent. It is used in the preparation of tinc-
is used as a fuel, pyri- ture of iodine, paints, essences, perfumes and cosmetics. It is also found in
dine, which has a bad drinks, spirit and cologne. Ethyl alcohol is the starting substance for most organ-
odor and dyes are
used. This mixture is ic compounds.
known as spirit.
Burning of ethyl alcohol reaction given as follow

C2H5OH + 3O2 o 2CO2 + 3H2O + 1374 kJ

Ethyl alcohol can burn very well therefore it can be used in internal combustion
engines.

Ethyl alcohol is used in antifreeze products, and also as a fuel a solution of

70–85% of ethyl alcohol is commonly used as a disinfectant. It kills organisms by
denaturing their proteins and dissolving their liquids and it is effective against
most bacteria, fungi and many viruses though ineffective against bacterial
spores.

Ethyl alcohol which is taken into the body via alcoholic beverages slowly causes
permanent, harmful effects. Alcohol copies water molecules and takes their
place in the brain, causing changes in the nervous system.

Synthesis
To synthesize ethyl alcohol, many methods may be used. Some of these methods
are;
Ethyl alcohol produced by the fermenta- 1. By Fermentation
tion process is purified by fractional dis-
tillation. Most ethanol is prepared by the fermentation of sugar. It can be fermented by;

a. Plants containing starch: Wheat, corn, potato, oats, etc.

b. Plants containing sugar: Sugarbeet, sugarcane and fruits.

42 Oxygen And Nitrogen Containing Organic Compounds

In the fermentation process, carbohydrates in these sources are converted into
simple sugars (glucose and fructose) and then these are converted into alcohol
and carbon dioxide.
maltase
C12H22O11 + H2O o 2C6H12O6
maltose glucose
zymase
C6H12O6 o 2C2H5OH + 2CO2
glucose ethyl alcohol

2. From Ethene Yeast is added to glucose solution and

it is allowed to ferment. CO2 gas pro-
Ethyl alcohol for industrial purposes is produced by hydrating ethene using a phos- duced by fermentation clouds the
phoric acid catalyst. This process costs less than fermentation. Ca(OH)2 solution in the test tube.

300°C
C2H4(g) + H2O(g) o C2H5OH(l)
pressure
ethene ethyl alcohol

3. By Acetaldehyde
H
Ni
CH3 C O + H2 CH3 C H

H OH
acetaldehyde ethyl alcohol
When ethyl alcohol is burned in a porce-
lain cup, a pale yellow flame is
observed.

20
Complete the following reactions.
H2SO4
a. Ethyl alcohol + potassium o d. Ethyl alcohol o
140 °C
b. Ethyl alcohol + acetic acid o e. Ethyl alcohol + hydrogen iodide o
H2SO4
c. Ethyl alcohol o [O] [O]
180 °C f. Ethyl alcohol o .......... o

Alcohols and Ethers 43

 a. C2H5OH + K o C2H5OK +1/2 H2
H+
b. C2H5OH + CH3COOH o CH3COOC2H5 + H2O
H2SO4
c. C2H5OH o C2H4 + H2O
180 °C

H2SO4
d. 2C2H5 OH o C2H5 O C2H5 + H2O
140 °C

e. C2H5OH + HI o C2H5I + H2O

[O] [O]
f. C2H5OH o CH3 CHO o CH3 COOH
–H2O

21
How many grams of ethyl alcohol can be prepared from 200 grams of 80% pure
calcium carbide by a 75% yield reaction? (CaC2 : 64 g/mol, C2H5OH : 46 g/mol)

CaC2 + 2H2O o Ca(OH)2 + C2H2

C2H2 + H2O o CH3CHO
CH3CHO + H2 o CH3 CH2 OH
If the equations are added together
CaC2 + 3H2O + H2 o CH3 CH2 OH + Ca(OH)2
is obtained.
mass of CaC2 = 200 . 0.80 = 160 g
160 g
number of moles of CaC2 = n = ————— = 2.5 mol
64 g/mol
According to the equation, 1 mole of CaC2 produces 1 mole of ethyl alcohol. It
means that from 2.5 mol of CaC2, 2.5 mole ethyl alcohol can be produced.
Mass of ethyl alcohol :
m = n . M = 2.5 . 46 g/mol = 115 g
It is known that the reaction has a 75% yield. So,
115 g ethyl alcohol 100% yield
xg 75% yield
————————————————————
x = 86.25
In this process 86.25 g ethyl alcohol can be produced.

44 Oxygen And Nitrogen Containing Organic Compounds

6.3. GLYCOL
Alcohols containing two OH groups are called glycols. The most important
example is ethylene glycol, C2H4(OH)2. The IUPAC name of ethylene glycol is
1,2 – ethanediol.

Ethylene glycol is a colorless, odorless, syrupy liquid. It is completely miscible

with water. Since it has a low freezing point it is used as antifreeze in automobiles.
A high boiling point (197 °C) and heat of vaporization also makes it useful for this
purpose. It is also used in hydraulic brake fluid in cars and as a paint, oil, ink and
resin solvent.
Glycol has a freezing point of –115 °C
Ethylene glycol is a primary dihydric alcohol. It produces oxalic acid and various and is used in automobile radiators as
side-products when it is oxidised. antifreeze.
CH2 OH [O] H C O [O] COOH

OH – H2O OH OH
CH2 CH2 CH2
ethylene glycol glycol aldehyde glycolic acid

[O] COOH [O] COOH

– H2O
H C O COOH
glyoxalic acid oxalic acid

Glycols can be prepared by the reaction of ethylene dichloride and water;

CH2 Cl CH2 OH
+ 2H2O + 2HCl
CH2 Cl CH2 OH
1,2 – dichloroethane 1,2 – ethanediol Alfred Bernhard Nobel
(ethylene dichloride) (glycol) (1843 – 1896)
Alfred Nobel was born in 1833 in
Stockholm, Sweden. His family was
22 descended from Olof Rudbeck, the
best-known technical genius from
A member of the dialcohols reacts with excess sodium metal to produce 37 grams Sweden's 17th century era when it was
of an alkoxide and 5.6 L of H2 gas at STP. Find the molecular formula of the alco- a great power in northern Europe.
hol used. Nobel invented dynamite in 1866 and
later built up companies and laborato-
ries in more than 20 countries all over
the world.
The general reaction of dialcohols with Na metal: On November 27, 1895, Nobel signed
CnH2n+2O2 + 2Na o CnH2n(ONa)2 + H2 his last will providing for the establish-
ment of the Nobel Prize. He died of a
5.6 L cerebral haemorrhage in his home in
nH = —————— = 0.25 mol of H2 gas is produced.
2 22.4 L/mol San Remo, Italy on December 10,
1896.

Alcohols and Ethers 45

 According to the equation 1 mol H2 is produced with 1 mol alkoxide compound.

So the number of moles of alkoxide is 0.25 mol.

m 37
M of alkoxide is = —— = ——— = 148 g/mol
n 0.25

CnH2n(ONa)2 = 148 g/mol

12n + (2n . 1) + (16 + 23) . 2 = 148

n=5
The alkoxide compound has 5 carbon atoms.

The general formula of a dialcohol is

CnH2n+2O2

So the formula is

C5H12O2.

LIFE IN THE POLES

Antifreeze is a liquid cooling agent used in gasoline and diesel engines. Compounds are added to the water to reduce the
freezing point of the mixture. In the bodies of polar animals, some chemicals behave as an antifreeze.
The cold seas of the polar regions have water temperatures below freezing
point. For example, in the Antarctic seas, the water temperature is between
–1 °C to –4 °C.
The water temperature varies very little and without adaptation, fish
would freeze to death because of the high water content of blood and
flesh.
Also, all terrestrial insects are cold–blooded animals.
That means their body temperature changes with changes in the envi-
ronment. If the outside temperature decreases to –20 °C, their body
temperature also decreases to this same temperature.
At this temperature insects normally cannot survive, though an excep-
tion to this is an insect species living in the North Pole. These insects protect
themselves from the freezing cold by secreting a kind of antifreeze glycerol.
Polar animals produce sorbitol or glycerol in their body when the weather gets colder and decrease the amount of water in
their body. A polar insect can survive at –87 °C by using its antifreeze.

46 Oxygen And Nitrogen Containing Organic Compounds

6.4. GLYCERINE
Glycerine is the simplest trihydric alcohol, also
Molecular model
known as glycerol. The IUPAC name of glycerine of glycerine
is 1, 2, 3–propanetriol. Glycerine freezes at 18 °C,
boils at 290 °C and has a density of 1.261 g/ml.
Glycerine mixes with water, methanol and ethanol
in all proportions. It is a nonpoisonous, syrupy liq-
uid and it absorbs moisture well.

Glycerine is obtained as a co-product from the

hydrolysis of vegetable oils or animal fats. From
the esterification of glycerine with nitric acid, the
inorganic trinitrate ester (trinitroglycerine) is pro-
duced.

CH2 OH CH2 O NO2

H2SO4 Glycerine reacts with potassium
CH OH + 3HONO2 CH O NO2 + 3H2O permanganate.
CH2 OH CH2 O NO2
glycerine nitric acid trinitroglycerine

This reaction is exothermic. The reaction mixture is cooled by stirring and passing
an air current though it as this product (trinitroglycerine) explodes when it is struck
or heated to 45 °C. Dynamite is obtained when trinitroglycerine is absorbed by saw-
dust and kieselguhr (a sand-like substance with tiny pores).

It is a useful explosive and is an invention of Alfred Nobel, a Swedish scientist.

Glycerine is used as a moisturizing substance in tobacco, shaving and toilet

soaps, cosmetics and lotions, and in the manufacture of plastics, cellophane,
water colors, printing-press ink, ointment, antifreeze and dynamite.

Glycerine can be prepared by any of the general methods for preparing alcohols
but this is not economic. Cheap glycerine is obtained when fats and oils are Trinitroglycerine is used in making dyna-
hydrolyzed in a basic medium or by the fermentation of sugars. mite.

7. INTRODUCTION TO ETHERS
An ether can be considered as an alcohol derivative resulting from the conden-
sation of alcohols.
O O O
H H R H R R¢
water alcohol ether

Alcohols and Ethers 47

 Ethers having the same R groups bonded to oxygen are called simple or sym-
metric ethers, with different R groups present, they are known as asymmetric or
complex ethers.
H3C O CH3 CH3 O C2H5
simple (symmetric) ether complex (asymmetric) ether

O O
The (R ) groups in an ether molecule may be alkyl, alkenyl, alkynyl or aryl
H2C CH2 groups.
ethylene oxide tetrahydrofurane CH3 CH2 O CH3 H3C O CH2 CH CH2
Ethers may have a cyclic structure, such ethyl methyl ether allyl methyl ether
as ethylene oxide and tetrahydrofurane.
Ethylene oxide is a gas at room temper- O CH3
ature and is used as a disinfectant for
foods and a fungicide in agriculture.
methyl phenyl ether

The general formula of ethers is CnH2n+2O and so they are isomers of monohy-
dric alcohols with the same number of carbon atoms. Since there have to be at
least two carbons in an ether, there is no isomer of methanol which contains only
one carbon.

23
Write the molecular formula of the ethers which are isomers of the following alco-
hols.
a. CH3 CH2 OH
b. CH2 CH CH2 OH

c. CH2 OH

a. The isomer of a monohydric alcohol with two carbon atoms is dimethyl ether
which also has two carbons. The molecular formula of dimethyl ether is,
CH3 O CH3

b. CH2 CH O CH3

c. In benzyl alcohol, there is a benzene ring and a carbon atom. Therefore, a

benzene ring and an alkyl group with one carbon atom must be found in the
isomer of benzyl alcohol. It is methyl phenyl ether.

The molecular formula is O CH3

48 Oxygen And Nitrogen Containing Organic Compounds

8. NOMENCLATURE OF ETHERS
8.1. COMMON NAMES
When we name ethers we note to the functional groups attached to the oxygen
atom. After naming these groups in alphabetical order we add the word “ether”.
If the groups are symmetric in the ether, the prefix, di–, is written before the name
of the group.

CH3 CH2 O CH3 CH3 O CH CH2 O CH3

ethyl methyl ether methyl vinyl ether methyl phenyl ether

CH3 CH2 O CH2 CH3 CH3 O C (CH3)3 O

diethyl ether tert-butyl methyl ether diphenyl ether

24
Write the common names of the following ethers.
a. H3 C b. CH2 CH O CH CH2
CH O C 2 H5
H3 C
c. CH3 d.
O C2H5
CH3 C O CH3

CH3
CH3
e. CH3 CH2 O CH CH2 f.
O C CH3
CH3

a. Ethyl isopropyl ether b. Divinyl ether

c. Tert-butyl methyl ether d. Ethyl phenyl ether

e. Ethyl vinyl ether f. Tert-butyl phenyl ether

Alcohols and Ethers 49

 8.2. IUPAC SYSTEM
Ethers are named according to the “alkoxy alkane” (RO– R+) form in system-
atic naming. The number of the carbon atom to which the alkoxy group (RO–) is
attached is indicated.
2 1
CH3 O CH3 CH3 CH2 O CH CH3
methoxymethane 3
CH3
2 – ethoxypropane

25
Give the IUPAC name for the following compounds.
CH3
O CH3
a. O CH CH3 b. CH3 C O CH3 c.
CH3 CH3
Br

O C2H5
d. CH2 C O CH3 e. CH3 O CH CH3 f.
CH3 CH3 Cl Cl

g. CH3 CH2 O CH CH2

a. 2 - phenoxypropane
b. 2 - methoxy - 2 - methylpropane
c. 1 - methoxy - 3 - bromobenzene
d. 2 - methoxypropene
e. 2 - methoxypropane
f. 1 - ethoxy - 2,4 - dichlorobenzene
g. Ethoxyethylene

9. PHYSICAL PROPERTIES OF ETHERS

Since the bond angle, R O R, is not equal to 180 °C in ethers, they show
limited polarity. Increasing the size of the R groups decreases the polarity of
ethers.
O
110°
R R

50 Oxygen And Nitrogen Containing Organic Compounds

Since ethers do not have a hydrogen atom bonded to the oxygen, they do not
undergo hydrogen bonding between their molecules. Therefore, ethers are more
volatile than their corresponding alcohols.
H3C O CH3 CH3 CH2 OH
dimethyl ether ethyl alcohol
b.p : – 24.9 °C b.p : 78.3 °C

The boiling points of ethers increase as their molar masses increase.

Like other organic compounds, branching lowers the boiling points of ethers.
Since ethers are polar, they dissolve in water by forming hydrogen bonds. The
solubility of ethers decrease when the molar masses increase. Ethers dissolve
many polar and nonpolar substances very well.

Melting Boiling Density

Name Formula
Point (°C) Point (°C) (g/mol)
Dimethyl ether CH3OCH3 – 138 – 24.9 0.661
Diethyl ether CH3CH2OCH2CH3 – 116 34.6 0.714
Dipropyl ether (CH3CH2CH2)2O – 122 90.5 0.736
Diisopropyl ether (CH3)2CHOCH(CH3)2 – 86 68.0 0.735
Methyl butyl ether CH3(CH2)3OCH3 – 116 70.3 0.744
Dibutyl ether (CH3CH2CH2CH2)2O – 95 141.0 0.769
1,2-dimethoxyethane CH3OCH2CH2OCH3 – 68 83.0 0.863
Anisole C6H5OCH3 – 37.3 158.3 0.994
(methoxybenzene)

Table 2: Physical properties of some ethers

26
Put the following compounds in order of decreasing boiling points,
I. CH3 CH2 CH2 CH2 OH

II. CH3 CH2 O CH2 CH3

III. CH3 O CH CH3

CH3

Since all the compounds have the same molecular formula, C4H10O, their molar
masses are equals, so there is no difference in boiling points due to the molar mass-
es. These molecules are members of different classes.

Alcohols and Ethers 51

 The first one is an alcohol, the second and the third ones are ethers. Alcohols
have higher boiling points than ethers because of their hydrogen bonding. Since
the third compound has branching, it has a lower boiling point than the second
ether compound.
So the decreasing order of boiling points is I > II > III.

10. CHEMICAL PROPERTIES OF ETHERS

In ethers, the oxygen atom is attached to two carbon atoms. Therefore, chemi-
cally, ethers resemble alkanes rather than water or alcohols.
Ethers are stable and do not have an affinity for bases, oxidants or reductants. In
this respect, they behave like alkanes and differ from alcohols.

When ethers are heated with concentrated strong acid halides they undergo
decomposition reactions. Alcohols and alkyl halides are the products.
R O R+H X o R O H+R X
C2H5 O C2H5 + HI o C2H5OH + C2H5I

27
0.2 mole of diethyl ether reacts with a sufficient amount of concentrated HBr solu-
tion. How many grams of which alcohol is obtained at the end of the reaction?
(C2H5OH : 46 g/mol)

The reaction of diethyl ether with concentrated HBr solution is:

C2H5 O C2H5 + HBr o C2H5OH + C2H5Br
1 mol of ethyl alcohol is produced from 1 mol of diethyl ether. From 0.2 mol of
diethyl ether, 0.2 mol of ethyl alcohol is produced. Molar mass of C2H5OH is 46
g/mol.
m m
n = –––––– then, 0.2 = –––––––––––––
M 46 g/mol
m = 9.2 grams of ethyl alcohol is obtained.

Ethers are flammable substances. Simple members of the aliphatic ethers are
particularly volatile, because of this if ethers are used in a laboratory, care must
be taken if there are any flames present.
3n
CnH2n+2O + –––– O2 o nCO2 + (n+1)H2O
2
C2H5 O C2H5 + 6O2 o 4CO2 + 5H2O

52 Oxygen And Nitrogen Containing Organic Compounds

 28
How many grams of diethyl ether can be burned in 336 L of air at STP?
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

The combustion reaction of diethyl ether is:

C2H5OC2H5 + 6O2 o 4CO2 + 5H2O
Mol number of air used:
336
n = ––––––– = 15 mol
22.4
20
Since 20 percent of air is oxygen, 15 . ––––––– = 3 mol oxygen is used in the
reaction. 100
According to the equation, 6 mol of oxygen reacts with 1 mol diethyl ether. For
3 mol of oxygen 0.5 mol of diethyl ether is required.
M of diethyl ether : C2H5OC2H5 = (4 . 12) + (10 . 1) + 16 = 74 g/mol
Mass of diethyl ether : m = n . M = 0.5 . 74 = 37 g

11. PREPARATION OF ETHERS

Ethers are generally synthesized by two methods.

Dehydration of Alcohols
When alcohols are dehydrated in the presence of a H2SO4 catalyst, alkenes or
ethers are produced. The temperature of the reaction medium determines
whether the product is an alkene or ether. Formation of an ether takes place at a
lower temperature than the formation of an alkene.
H2SO4
2R OH o R O R + H2O
140 °C
alcohol ether
H2SO4
2CH3 OH o H3C O CH3 + H2O
140 °C
methanol dimethyl ether

+ + +
R OH + H R O H R + H2O
H
+ +
R +R O H R O R +H

Only symmetrical ethers can be obtained from these reactions proceeding in the
presence of an acid catalyst.

Alcohols and Ethers 53

 The Williamson Synthesis of Ethers
This method is used in the presence of a basic catalyst to produce both symmetri-
cal and unsymmetrical ethers. The reacting substances in these reactions are alkyl
halides and metal alkoxides. By using the correct reactants, desired ethers may be
obtained. Metal halide salts are produced as co-products.
R X+R O– Na+ o R O R + NaX
C2H5 I + C3H7 O– Na+ o C2H5 O C3H7 + NaI

– +
CH3 Br + O K O CH3 + KBr

potassium phenoxide methyl phenyl ether

12. DIETHYL ETHER

Diethyl ether is the most commonly known ether and is called simply “ether” in
daily life.
Diethyl ether is a colorless, volatile, flammable liquid with a characteristic pleas-
ant odor. It causes fainting when inhaled, which explains its use as an anaesthet-
ic in medicine.
Diethyl ether is a good solvent for organic compounds and is also used to
remove H2O in organic reactions.
Diethyl ether is also used both in the Wurtz synthesis and in the preparation of
Grignard Reagents.
In the laboratory ether is produced by dehydrating 1 mole of H2O from 2 moles
of ethyl alcohol.
H2SO4
2C2H5OH o C2H5OC2H5 + H2O
140 °C
ethyl alcohol diethyl ether

Diethyl ether is a highly flammable liquid. Take care when you use ethers in the
laboratory.

54 Oxygen And Nitrogen Containing Organic Compounds

1. Write the structural formulae of the following com- h. Br CH2 CH2 OH
pounds
OH
a. Isopropyl alcohol
b. Isobutyl alcohol
i. HO CH2OH
c. Cyclobutanol
d. Tert-pentanol
e. Glycol OH
f. Neo-pentanol j.
CH3
g. 3-ethyl-3-methyl-2-pentanol
h. 2,2-dimethyl-1,4-hexandiol
i. 1,3-butandiol
j. 3-butene-1-ol 3. Arrange the following compounds in order of decreasing
melting points.
k. 3,3-dichlorocyclohexanol
I. CH3CH2OH II. CH3CH3 III. HOCH2CH2OH

2. Give the names of the following compounds.

4. Write the structural formulae and the names of the alco-
a. CH3 CH2 CH CH3 hols which have the molecular formula of
OH a. C3H8O

b. CH3 CH CH CH3 b. C4H10O

OH CH3
5. Explain the primary, secondary and tertiary alcohol
c. CH3 CH (CH2)4 OH
terms by giving an example of each.
CH3

d. CH3 6. Classify the given alcohols as primary, secondary or ter-

CH CH2 OH tiary.
CH3
C2H5

e. CH3 CH2 CH2 CH3 a. C2H5 C OH b. OH

C C2H5
CH3 CH2 OH
OH
OH c. CH3 CH OH d.
CH3
f. HO CH2 CH2 CH2 C CH3 CH3

g. HO CH2 CH CH2 OH 7. Explain the terms monoalcohols, dialcohols and trialco-

OH hols by giving an example for each of them. Give their
general formulae.

Alcohols and Ethers 55

8. Why do alcohols show both polar and nonpolar proper- d. C2H5OH + HI o
ties. Explain. heat, pressure
e. CH3CH2CH CH2(g) + H2O o
9. While the solubility of isobutyl alcohol is 100g/100 cm3 catalyst
of H2O, that of ethyl alcohol is infinite. Explain why. f. CH3OH + HCOOH o

10. When 0.05 mol of a monoalcohol is burned, 2.2 grams g. CH3CH2CH2OH + CH3Br o
of CO2 is produced. How many liters of oxygen gas are +HCl
used at STP? (CO2 : 44 g/mol) h. CH3 C O + CH3MgCl o o
–MgCl2
H
11. If 5.4 grams of H2O is added to a sample of an alkene,
+HCl
26.4 grams of a monoalcohol is obtained. What is the i. C3H7 C O + C2H5MgCl o o
molecular formula of the alcohol? –MgCl2
CH3
12. When 13.8 grams of a primary alcohol reacts with Na
j. OH + K2Cr2O7 + H2SO4 o
metal, 3.36 L of H2 gas is evolved at STP.
a. Find the molecular formula of the alcohol.
b. Name the product.

13. 10 gram of 2-butanol is oxidised by an excess amount of
acidic KMnO4 solution and the reaction occurs with 74%
efficiency. What is the mass and molecular formula of
the substance produced?
14. How many grams of ethanal are obtained when 69 grams
of ethyl alcohol are oxidised?
k. C3H5(OH)3 + O2 o
20. When 106 grams of a mixture of cyclopentanol and
water reacts with excess Na, 44.8 L of H2 is produced at
STP. Find the mole percentage of cyclopentanol in the
mixture.

15. I. If water is added to 2-butene, product A is obtained. 21. What are the factors that affect the solubility of alcohols
II. At the end of the oxidation of A, compound B is in water?
obtained.
Give the products A and B. 22. What are the meanings of simple and complicated
ethers? Explain with examples.
16. 6.3 grams of propylene reacts with water. The formed
substance is added to an excess amount of KMnO4
23. Give the IUPAC and common names of the following
under heat and acidic media.
compounds
How many grams of product is formed?
a. CH3 CH2 O CH2 CH3
17. What possible products can be obtained if cyclopentanol b. CH3 CH2 O CH2 CH2 CH3
is heated in concentrated H2SO4 solution?
c. CH3 CH O CH CH3
18. How many alcohols with the molecular formula C5H12O CH3 CH3
can be found? Give their structural formulae.
d. O CH2
19. Complete and balance the following equations.
a. C2H5OH + O2 o
O
b. CH3CH2CH2 Cl + NaOH o e.

c. CH3OH + K o

56 Oxygen And Nitrogen Containing Organic Compounds

24. Write the molecular formulae of the following com- 34. Which of the following are ethers?
pounds.
a. CH3CH2 O CH2CH3
a. Methyl isopropyl ether
O
b. Ethyl phenyl ether
c. Dipropyl ether b. CH3CH2 O C CH2CH3

d. Divinyl ether
c. OH

25. What is the molecular formula of the simple ether that

contains 52.17% carbon, 34.78% oxygen and 13.04% d. O CH2CH3
hydrogen by mass?
O
e.
26. If a 73 gram mixture of ethyl alcohol and diethyl ether is
burned, 85.12 L of CO2 gas is produced at STP. What is
O
the mass percentage of diethyl ether in the mixture? f.
H2C CH2

27. If a 25 gram mixture of methanol and diethyl ether is

treated with sodium metal, 5.6 L of H2 gas is evolved at
35. Give the products if the following compounds are heat-
STP. ed in a strong acidic medium at 140 °C.
What is the mass percentage of ether in the mixture?
a. n-butanol
b. cyclopentanol
28. Equal masses of acid and monoalcohol react to give 51 c. 2,2-dimethylbutanol
g of an ester and 0.5 mol water. Find the molar mass of
the alcohol.
36. Which alcohols are used as reactants to produce the fol-
lowing ethers?
29. Write the equations of each step for the oxidation of a. CH3CH2 O CH2CH3
methanol.
b. CH3 CH O CH CH3

30. Why is methyl alcohol is known as wood alcohol? Explain. CH3 CH3

O
31. Why is glycol preferred as antifreeze in automobiles over c.
ethyl alcohol? Explain.

d. CH3 CH2 O CH CH3

32. What is the main reason of using glycerine in soaps and
cosmetics? Explain. CH3

33. Write the names of following compounds.

37. Arrange the following compounds in the order of
a. CH3 CH2 O CH2 CH3 decreasing boiling point.
b. CH3 CH2 CH2 O CH2 CH CH2 I. CH3CH2CH2 OH
c. CH3 O CH CH2 II. HO CH2CH2CH2 OH
d. O
III. CH3CH2CH3
H2C CH2
IV. CH3CH2 O CH3

Alcohols and Ethers 57

1. C2H5
5. Which one of the following compounds is not an isomer
of the others?
CH3 C CH C2H5
A) CH3CH2CH2CH2OH
OH CH3
B) CH3 O C3H7
Which one of the following names is correct for the given
C) C2H5 O C2H5
compound?

A) 2–hydroxy–2–ethyl–3–methylpentane D) CH3 CH CH2 CH3

B) 3–hydroxy–3–methyl–4–ethyl OH
C) 3–hydroxy–3–methyl–4–ethyl
E) CH3 CH OH
D) 3–hydroxy–3,4–dimethylhexane
E) 4–hydroxy–3–methylpentane CH3

2. Which one of the following bonds is not found in the 6. CH3 O C2H5
structure of alcohols?
For the given compound,
A) C C B) C H C) H O I. It is ethyl methyl ether.
D) C O E) H H II. Hydrogen bonds exist between the molecules of the
compound.
III. It is an isomer of iso-propyl alcohol.
Which of the above statements above is/are true?

3. Which one of the following alcohols doesn’t have an A) I only B) I and III C) II and III
ether isomer? D) I and II E) I, II and III

A) CH3OH B) C2H5OH C) C3H7OH

D) C4H9OH E) C5H11OH

7. I. CH3OH

II. H C O
4. What is the name of the hydrocarbon in which two
methyl, one ethyl and one hydroxy group are attached to H
a carbon atom? III. CH4

A) 2– methyl – 2 – butanol Which of the following gives the correct comparison for
B) 2– methyl – 2 – hydroxy– propane the above compounds with respect to their boiling
points?
C) 2,2 – dimethyl – 2 – hydroxy – propane
D) n – pentanol A) I > II > III B) III > II > I C) I = II = III
E) 2– pentanol D) II > I > III E) III > I > II

58 Oxygen And Nitrogen Containing Organic Compounds

8. I. Isopropyl alcohol and dimethyl ether 11. I. n-pentanol
II. 2 – butanol and ethyl methyl ether II. Isopentanol
III. 3 – pentanol and ethyl propyl ether III. Neopentanol
Which of the given pairs of compounds are isomers? Which is true for the melting point comparison of the
above compounds?
A) I only B) II only C) III only
D) II and III E) I, II and III A) I = II = III B) I > II > III C) I > III > II
D) III > I > II E) III > II > I

9. What is the molecular formula of the monoalcohol that

contains 60% carbon by mass?
12. At least how many carbon atoms are found in a tertiary
A) CH3OH B) C2H5OH C) C3H7OH alcohol?
OH A) 1 B) 2 C) 3 D) 4 E) 5
D) E) OH

10. CH3

CH3 C CH3
13. Some compounds and their first oxidation products are
OH given below.
Compound Oxidation product
Which of the names below can be used to correctly ————————— —————————
name the above compound? I. Primary alcohol Aldehyde
I. Isobutanol II. Secondary alcohol Ketone
II. Tertiary butanol III. Tertiary alcohol Carboxylic acid
III. Trimethyl carbinol Which is/are correct?

A) I only B) II and III C) III only A) I only B) I and II C) II and III

D) I and II E) I, II and III D) III only E) I, II and III

Alcohols and Ethers 59

14. When ethyl alcohol is oxidised by two degrees, which 17. Which one of the following compounds is produced by
one of the following products results? the primary oxidation of butane-2-ol?

A) Acetaldehyde B) Acetic acid A) Ethyl methyl ketone

C) Oxy-propane D) Dimethyl ether B) Dimethyl ketone
E) Dimethyl ketone C) 2-butanol
D) Butanoic acid
E) Diethyl ketone

15. While using an equal mass of ethyl alcohol, the follow-

ing substances are produced.
I. Ethylene
II. Ethane
III. Acetic acid 18. For the given compounds having the same number of
carbon atoms;
Which one of the given comparison is true, if the mass
of products are compared? I. Primary alcohol
II. Secondary alcohol
A) I>II>III B) III>II>I C) I=II=III
III. Tertiary alcohol
D) II>III>I E) III>I>II
Which one is true for their boiling point comparison?

A) I > II > III B) I = II = III C) III > II > I

D) I > III > II E) III > I > II

16. CH2 CH CH2 OH

For the given compound,
I. Its aqueous solution has basic properties.
II. It forms esters with carboxylic acids. 19. From the reaction of 4.6 grams of a monoalcohol with
III. It fades the color of an aqueous solution of bromine. Na metal, 1.12 L of H2 gas is obtained at STP. What is
Which of the above statements is/are true? the molar mass of the other product obtained?
(C : 12, H : 1, O : 16, Na : 23)
A) I only B) III only C) I and II
D) II and III E) I, II and III A) 45 B) 46 C) 68 D) 70 E) 72

60 Oxygen And Nitrogen Containing Organic Compounds

20. 2.24 L of H2 gas is evolved after the reaction of a 20 23. CH2 CH CH2
grams mixture of C2H5OH and CH3OCH3 with Na metal.
OH OH OH
What is the mass percentage of dimethyl ether in the For 1 mole of the above organic compound,
mixture?
I. It reacts with 3 mol of Na.
A) 46 B) 54 C) 82 D) 18 E) 72 II. When 1 mol is reacted with a sufficient amount of Na
metal, 3/2 mol of H2 gas is evolved.
III. It reacts with 1 mol of Zn.
Which of the above statements is/are true?

A) I only B) II only C) I and II

D) I and III E) I, II and III

21. In acidic medium, CH3OH reacts with KMnO4 solution,

to give the following reaction:
24. [O] [O] [O]
5CH3OH + 4KMnO4 + 6H2SO4 o C2H5OH o X o Y o 2Z + 2H2O
–H2O
5HCOOH + 4MnSO4 + 2K2SO4 + 11H2O
For given reaction,
How many grams of CH3OH react with 400 mL, 0.1 M
I. The compound X is acetaldehyde.
KMnO4 and how many grams of HCOOH are produced
II. The compound Y is acetic acid.
by the reaction?
III. The compound Z is carbon dioxide.
CH3OH HCOOH Which of the above statements is/are true?
––––––––––– ––––––––––––– A) I only B) II only C) I and II
A) 1.6 2.30 D) II and III E) I, II and III
B) 3.2 4.60
C) 1.6 1.15
D) 2.4 3.45
E) 4.8 2.30
25. CH3

CH3 C C2H5

OH

For the above compound, which one of the following

names cannot be used?

A) 2–methyl–2–butanol
22. How many liters of CO2 gas are produced by the com- B) 2–methyl–2–hydroxybutane
bustion of 0.5 mole of diethyl ether with a sufficient C) Tertiary pentanol
amount of oxygen gas?
D) Dimethyl ethyl carbinol
A) 44.8 B) 22.4 C) 16.8 D) 8.96 E) 5.6 E) 2-pentanol

Alcohols and Ethers 61

 SOLVE AND FIT PUZZLE
Solve the clues and place your answers in their correct positions in the grid. A few letters have been put into the grid to start you off.

M
G T
O G
N O
C

P A L

C D D E

G
K E

C X
D

18 – LETTER WORDS 8 – LETTER WORDS

– Alcohols containing two or more hydroxyl groups in their
molecules are called __________________
– Ethers are isomers of these compounds.
16 – LETTER WORD
– These alcohols can not be oxidized because they do not
have a H atom on the carbon atom bearing the –OH
group
15 – LETTER WORDS
– In the second oxidation of primary alcohols these com-
pounds are produced.
– This describes compounds in which the carbon that bears
the –OH group is attached to only one other carbon.
9 – LETTER WORDS
– In the first oxidation of primary alcohols these compounds
are produced.
– The IUPAC name of this compound is 1, 2, 3, propanetri-
ol.
– Boiling points of ethers ____________ as their molar
masses increase
– This describes compounds whose molecules have a
hydroxyl group attached to a saturated carbon atom
– The simplest alcohol
– Alkyl magnesium halides (R–Mg–X) are also known as
____________ reagents
7 – LETTER WORD
– These compounds are formed when secondary alcohols
are oxidised.
6 – LETTER WORDS
– Since it has a low freezing point it is used as antifreeze in
automobiles.
– This describes compounds in which an oxygen atom is
attached to two carbon atoms.
– Ethers that have the same alkyl groups bonded to the oxy-
gen atom are called ________________ ethers.

62 Oxygen And Nitrogen Containing Organic Compounds

 INTRODUCTION
The C O group is known as the carbonyl group in organic compounds.

Some Greek Letters This group is found in aldehydes, ketones, carboxylic acids, esters and acid deriv-
Capital Small atives and is the main functional group in compounds such as amides.
Name
letter letter
————— ————— ————— In this group, the carbon atom is sp2– hydridized. As a result of the hybridization,
$ D Alpha three sigma (V) bonds and one pi (S) bond are formed. Sigma bonds, which lie
% E Beta in a plane with bond angles of 120°, are present between the carbon–oxygen and
* J Gamma
carbon-alkyl groups.
' G Delta
1 Q Nu Since the carbonyl group contains different atoms, it is polar. In the C O bond,
3 S Pi oxygen is much more electronegative than carbon and so, electron density in the
5 U Rho bond is displaced towards the oxygen atom. This results in the double bond elec-
6 V Sigma trons being shifted towards the oxygen atom.

C O
d+ d–

So in the carbonyl group, the oxygen atom is partially negative and the carbon
atom is partially positive. From X–ray experiments, the length of the C O bond
in the carbonyl group is found to be 1.22 A° .

1. ALDEHYDES
Compounds in which one hydrogen atom and one carbon atom are bonded to
the carbon atom in the carbonyl group are called aldehydes.

R
Aldehydes are represented by the general formula, C O or RCHO.
H

C O or CHO groups are the functional groups of aldehydes.

H
R may be an alkyl or aryl group. The general formula of aliphatic aldehydes is
CnH2nO. The simplest member of the aldehydes is formaldehyde and has two
hydrogen atoms bonded to the carbonyl group.

1
What is the molecular formula of the aldehyde that contains 40% carbon by
mass? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

64 Oxygen And Nitrogen Containing Organic Compounds

The molar mass of the aldehyde that has the molecular formula CnH2nO is
(12n + 2n + 16) or (14 n + 16) g/mol.
Mass of carbon is 12n gram.
As stated in the question 40% of the aldehyde by mass is carbon. So in 100
grams aldehyde there must be 40 grams carbon. To find the number of moles of
carbon, the following proportion is considered.
100 g aldehyde contains 40 g C
(14n+16) g aldehyde contains 12n g C
––––––––––––––––––––––––––––––––––––––––––––––––
40 · (14n + 16)
12n = –––––––––––––––––––– , so n = 1
100
If n = 1, the molecular formula is CH2O, formaldehyde.

2
What is the molecular formula of the aldehyde that has a density of 1.80 g/L at
room conditions? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol) (Hint : At room
conditions a mol of gas occupies 24.5 L)

d = 1.80 g/L means that 1 L of this aldehyde weighs 1.80 g. Since 1 mole of gas
occupies 24.5 L at room conditions, the mass of 24.5 L of aldehyde will give the
molar mass of the aldehyde.
M = 1.80 g/L · 24.5 L/mol # 44 g/mol
According to this, the molar mass of CnH2nO is 44 g/mol.
So, 12n + 2n + 16 = 44 and n = 2.
The molecular formula of the aldehyde is C2H4O .

2. NOMENCLATURE OF ALDEHYDES
The longest chain of carbon atoms containing the aldehyde group is selected,
and the chain is numbered assigning “1” to the carbon of carbonyl group.
Substituents attached to the longest chain are given names and numbers. The
name of the aldehyde is taken from the alkane with the same number of carbon
atoms by changing the –e ending to -al.:

Aldehydes and Ketones 65

 Many aldehydes also have common names

O O O O O
4 3 2 1
H C CH3 C C3H7 C C4H9 C CH3 CH CH C
H H H H H
methanal ethanal butanal pentanal 2 – butenal
formaldehyde acetaldehyde butyraldehyde valeraldehyde

3
H3 C O CH3 O O O
2 1
CH C CH3 C CH2 C C6H5CH2 C C
H3 C H CH3 H H H
2 – methylpropanal phenylethanal benzene carbaldehyde
3,3 – dimethylbutanal
phenylacetaldehyde benzaldehyde

The positions of substituents on the chain may be indicated by the letters D,

E, J, G in aldehydes beginning with the carbon atom closest to the aldehyde
group.
5
O H3C O
3 2 1 d 4 3 2 1
CH3 CH C CH CH2 CH2 C
b a g b a
CH3 H H3C H
a – methylpropanal g – methylpentanal

3
Name the following compounds.
CH3 O O CH3 O
a. CH3 CH2 C CH2 C b. CH3 CH C c. CH3 C C

CH3 H OH H C2H5 H

O C2H5 C2H5 O O
d. CH2 CH2 C e. CH3 C CH C f. CH3 CH CH C
H CH3 H OH C2 H 5 H

a. 3,3 – dimethylpentanal d. 3 – phenylpropanal

b. 2 – hydroxypropanal e. 2 – ethyl – 3,3 – dimethylpentanal
c. 2,2 – dimethylbutanal f. 2 – ethyl – 3 – hydroxybutanal

66 Oxygen And Nitrogen Containing Organic Compounds

 4
Write structural formulae of the following compounds.
a. Isobutanal
b. 2, 3, 4 – trihydroxybutanal
c. p – methylbenzaldehyde
d. 2 – bromopropanal

CH3 O O
a. CH3 CH C b. CH2 CH CH C
H OH OH OH H
O O
c. H3C C d. CH3 CH C
H Br H

3. PHYSICAL PROPERTIES OF ALDEHYDES

Because of the carbonyl group C O , aldehydes are polar molecules.

d+ H
In this structure, the oxygen atom is not bonded to a hydrogen, so there is no R d–
hydrogen bonding between aldehyde molecules. Consequently, they have lower O
C O H
boiling points than the corresponding alcohols but higher boiling points than the
–
d d+
corresponding ethers. d+ H

O d–
CH3 CH2 CH2 OH CH3 CH2 C CH3 CH2 O CH3 O
d+
H H d+
H
n – propanol propanal methoxy ethane
b.p. 97.2 °C b.p. 49 °C b.p. 10.8 °C
Low molar mass aldehydes dissolve in
Formaldehyde is a gas at room temperature. The C2 to C11 aldehydes are liquids water due to hydrogen bonding.
Hydrogen bonds are formed between
and aldehydes higher than C11 are solids at room temperature.
the oxygen atom of the aldehyde and the
The carbonyl oxygen atom allows molecules of aldehydes to form strong hydro- hydrogen atom of water and also
gen bonds with water molecules. As a result, low molar mass aldehydes show between the hydrogen atom of the alde-
hyde and the oxygen atom of water.
appreciable solubilities in water. As the molar mass increases, polarity decreases
because of the effect of the hydrocarbon groups, hence the solubility in water
also decreases.

Aldehydes and Ketones 67

 The lower molar mass aldehydes have a sharp odor, though the odor becomes
more fragrant as the molar mass increases. Thus, many aldehydes are used in
perfumes and for food flavoring.

Melting Boiling *Density Solubility

Name Formula
Point (°C) Point (°C) (g/mL) (g/100 mL water)

Formaldehyde (Methanal) HCHO – 92 – 21 0.815 very soluble

Acetaldehyde (Ethanal) CH3CHO – 125 21 0.783 very soluble

Propionaldehyde (Propanal) CH3CH2CHO – 81 49 0.806 very soluble

n – Butyraldehyde (Butanal) CH3(CH2)2CHO – 99 76 0.817 soluble

n – Valeraldehyde (Pentanal) CH3(CH2)3CHO – 91,5 102 0.810 slightly soluble

Caproaldehyde (Hexanal) CH3(CH2)4CHO – 51 131 0.833 slightly soluble

Benzenecarbaldehyde C6H5CHO – 26 178 1.42 slightly soluble
(Benzaldehyde)
* Densities are given according to 20°C.

Table 1: Properties of some aldehydes.

4. CHEMICAL PROPERTIES OF ALDEHYDES

Aldehydes have a high tendency to undergo chemical reactions because of their
polar carbonyl group. Aldehydes have a hydrogen atom attached to the carbonyl
group which makes them more active than ketones. Because this hydrogen
atom is held only loosely, aldehydes undergo oxidation reactions. Also aldehy-
des may undergo addition reactions by opening up the S bond in the carbonyl
group. Addition of hydrogen, a reduction, reaction is also possible. Let's exam-
ine the oxidation, addition, polymerization and combustion reactions of aldehy-
des.

4.1. OXIDATION REACTIONS

Aldehydes are readily oxidized, like alcohols, by strong oxidizing agents such as
KMnO4, K2Cr2O7 or K2CrO4 in the presence of acids. They form carboxylic
acids.
O O O O
[O] [O]
R C R C CH3 C CH3 C
H OH H OH
aldehyde carboxylic acid acetaldehyde acetic acid

68 Oxygen And Nitrogen Containing Organic Compounds

In addition to this, aldehydes are also oxidized by some oxidizing agents such as
Tollens’, Fehling's and Benedict's reagents. These reactions are characteristic reac-
tions of aldehydes.
Tollens' Reagent
Tollens’ Test (Silver Mirror Test)
Tollens' A : 3 g of AgNO3 is dissolved in
Mixing aqueous silver nitrate with aqueous ammonia produces a solution known 30 cm3 of water, and put in a dark col-
as Tollens’ reagent. The reagent contains the diamminosilver (I) ion (Ag(NH3)2+). ored bottle. Then it is closed tightly.
During the test silver is reduced from the +1 oxidation state to metallic silver as
Tollens' B : 3 g of NaOH is dissolved in
it oxidizes aldehydes to carboxylate ions. 30 cm3 of water, and put in a dark col-
O O ored bottle. Then it is closed tightly.
+ – +
R C + 2Ag(NH3)2 + 2OH R C + 2Ag¯ + NH4 + H2O + 3NH3 Equal volumes of Tollens' A and
H O – silver Tollens' B solutions are mixed. Diluted
mirror
aldehyde carboxylate ammonia is then added to the mixture
until the formed silver oxide dissolves.
This reaction can be shown more simply like this.
O O This solution should not be prepared
well in advance, or heated, otherwise a
R C H + 2Ag++ 3OH– R C O– + 2Ag¯ + 2H2O
black precipitate forms. The minimum
aldehyde carboxylate silver
mirror amount of NH3 should be used
Tollens' reagent reacts with some aldehydes in cold conditions and some alde-
hydes in hot conditions. Metallic silver, produced in the reaction, is deposited on
the walls of the vessel (silver mirror) or it precipitates. This reaction is used to
detect the presence of an aldehyde or to distinguish between aldehydes and
ketones.

a. b. c. a. Put the aqueous silver nitrate and aqueous

ammonia solutions into the clean beaker.

b. You can see that color of the solution dark-

ens. As ethanal is oxidized to ethanoic acid,
Ag+ ions are reduced to metallic silver.

c. Metallic silver is deposited on the walls of

the beaker as a mirror. All aldehydes under-
go this same reaction.

Silver mirror test

5
Write an equation for the reaction of each of the following with Tollens' reagent.
a. formaldehyde
b. acetaldehyde
c. benzaldehyde

Aldehydes and Ketones 69

 O O
–
Tollens’ Reagent a. H C H + 2Ag++ 3OH– H C O + 2Ag + 2H2O
formaldehyde formate ion
Bernard Tollens was German chemist
and in 1881 first used this complex sil- O O
ver solution to detect aldehydes. + – –
b. CH3 C H + 2Ag + 3OH CH3 C O + 2Ag + 2H2O
acetaldehyde acetate ion

+ –
c. C O + 2Ag + 3OH C O + 2Ag + 2H2O
–
H O
benzaldehyde benzoate ion

6
1 gram of a mixture of glycol-acetaldehyde reacts with Tollens' reagent to produce
1.08 g of a metallic silver. What is the percentage of acetaldehyde by mass in the
mixture? (C: 12 g/mol, H: 1 g/mol, O: 16 g/mol, Ag: 108 g/mol)

Tollens' reagent is a mild oxidizing agent so only acetaldehyde is oxidized in the

glycol-acetaldehyde mixture. As a result, metallic silver is produced. The equa-
tion for this reaction is as follows:
O O
+ –
CH3 C + 2 Ag + 3OH CH3 C + 2 Ag + 2H2O
–
H O

First let's find the mol number of Ag.

1.08 g
n = ––––––––––––– = 0.01 mol
108 g/mol

According to the equation, 1 mol acetaldehyde produces 2 mol Ag. To produce

0.01 mol Ag, 0.005 mol acetaldehyde must react. Molar mass of acetaldehyde;
CH3CHO : 44 g/mol. That means 1 mol acetaldehyde is 44 g and
0.005 mol acetaldehyde is equal to 44 g/mol · 0.005 mol = 0.22 g
So, we can find the percentage of acetaldehyde in the mixture.
in 1 g mixture 0.22 g acetaldehyde
in 100 g mixture xg
–––––––––––––––––––––––––––––––––––––––––––––––––––
x = 22 g
The percentage of aldehyde by mass in the mixture is 22% .

70 Oxygen And Nitrogen Containing Organic Compounds

Fehling’s Test
Fehling's solution is a basic solution of copper (II) ions complexed with sodium
or potassium tartrate. When Fehling's solution reacts with aldehydes Cu+2 ions,
which are a dark-blue color in the complex, are reduced to brick-red copper (I)
oxide (Cu2O). At the same time, the aldehyde is oxidized to the carboxylate ion
(RCOO–).

O O
R C + 2Cu+2 (complex)+ 5OH– (aq) R C + Cu2O(s) + 3H2O(l) Ethanal, which boils at 21°C, is the col-
– orless liquid in the test tube. Ethanal,
H dark – blue O brick – red
which evaporates in the test tube, pass-
aldehyde carboxylate
es over heated copper(II) oxide (CuO),
in the mouth of test tube, and turns into
Aromatic aldehydes are oxidized by Tollens' reagent, but not by Fehling's reagent.
ethanoic acid. The acid changes the
This property is used to distinguish between aliphatic and aromatic aldehydes.
color of the litmus paper held in the
mouth of test tube to red.

Fehling’s Reagent
Fehling's I : 34.64 grams of pure copper sulfate (CuSO4 . 5H2O) are dissolved in the
COO– –
OOC
minimum amount of water containing a few drops of H2SO4 . Then, the volume of
solution is diluted to 500 ml by adding water. CHOH HOHC
Cu+2
Fehling's II : 60 gram of NaOH and 173 grams Rochelle salt (sodium potassium tar- CHOH HOHC
trate, NaKC4H4O6) are dissolved in water and diluted to 500 mL. – –
COO OOC
The solutions when mixed are unstable so they should be in stored in separate bot-
CuC8H8O12
tles with the lid sealed tightly. When used, equal volumes of the solutions should be
mixed.

7
Write the reactions of Fehling's reagent with formaldehyde and acetaldehyde.

+2 –
H C O + 2Cu + 5OH H C O + Cu2O + 3H2O
–
H O
formaldehyde formate ion
+2 –
CH3 C O + 2Cu + 5OH CH3 C O + Cu2O + 3H2O
–
H O
acetaldehyde acetate ion

Aldehydes and Ketones 71

 8
10 grams of propanal solution react with Fehling's reagent to produce 11 grams
of Cu2O. What is the percentage of propanal by mass in the solution?

(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol, Cu : 63.5 g/mol)

Reaction equation;
O O
C2H5 C + 2Cu+2 + 5OH– C2H5 C + Cu2O + 3H2O
H O–
The molar mass of propanal = 58 g/mol.
The molar mass of Cu2O=143 g/mol.

to form 143 g of Cu2O 58 g of propanal is used

to form 11 of Cu2O x
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
x = 4.46 g propanal

There is 4.46 g of propanal in 10 g of solution. Percentage of propanal by mass

can be found by proportions.
in 10 g of solution 4.46 g of propanal is present
in 100 g of solution x g of propanal is present
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
x = 44.6
So there is 44.6% of propanal in the solution.

Reactions with KMnO4

Aldehydes reduce potassium permanganate. While the aldehyde is oxidized to a

carboxylic acid, Mn7+ in KMnO4 is reduced to the Mn2+ ion.

During the reaction, the violet color of potassium permanganate disappears.

– + cold 2+
5R C O + 2MnO4 + 6H 5R C O + 2Mn + 3H2O

H OH

9
3.6 grams of an aldehyde reacts with 100 mL of a 0.2 M of KMnO4 solution until
the color of the solution disappears. What is the molecular formula of the car-
boxylic acid produced? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

72 Oxygen And Nitrogen Containing Organic Compounds

The mol number of KMnO4 is n = M · V = 0.2 · 0.1 = 0.02 mol. The reaction
equation of an aldehyde with KMnO4 solution is;
– + 2+
5R C O + 2MnO4 + 6H 5R C O + 2Mn + 3H2O

H OH
–
According to the equation 2 mol of MnO4 reacts with 5 mol of aldehyde. So,
–
0.02 mol of MnO4 reacts with 0.05 mol aldehyde.
0.05 mol aldehyde is 3.6 g
1mol aldehyde is x
–––––––––––––––––––––––––––––––––––––––––––––
x = 72 g
29 g of 1 mol of aldehyde belongs to the functional group
(MCHO = 12 + 1 + 16 = 29 g/mol)
72 – 29 = 43 g belongs to the alkyl group.
CnH2n+1 = 43 g/mol.
So, 12n + 2n + 1 = 43 Ÿ 14n + 1 = 43 Ÿ n = 3
Since the alkyl group must be C3H7 , the molecular formula of the aldehyde is
C3H7CHO.
Since the aldehyde contains 4 carbon atoms, the produced carboxylic acid will
also have 4 carbon atoms in its structure. So the molecular formula of the car-
boxylic acid is C3H7COOH.

4.2. ADDITION REACTIONS OF ALDEHYDES

The most common reactions of compounds containing the carbonyl group are
addition reactions. In these reactions, the S bond in the carbonyl group C O
d+ d–
C O
is broken. Atoms or groups of atoms can bond with the carbon and oxygen atoms.
Because of the electronegativity differences, the carbon atom is partially positive
The electronegativity value of carbon is
(G+), and the oxygen atom is partially negative (G–).
2.5 and that of oxygen is 3.5.
So in addition reactions, positively charged (+) atoms or groups of atoms, bond
to the oxygen atom and negatively charged (–) ones bond to the carbon atom.

Addition of Hydrogen
Aldehydes react with H2 in the presence of a nickel platinum catalyst to form pri-
mary alcohols. The reaction is slow and occurs only under certain conditions.

Aldehydes and Ketones 73

 H
Ni, Pt
R C O + H2 R C OH
heat, pressure
H H
aldehyde primary alcohol

H
Ni, Pt
H C O + H2 H C OH
heat, pressure

H H
methanal methanol

Nowadays, metal hydrides are widely used to reduce aldehydes. The most impor-
tant are lithium aluminum hydride (LiAlH4) and sodium borohydride (NaBH4).
+
+ LiAlH4/ether H
R CH2OH
primary alcohol
R C O

H R CH2OH
+
+ NaBH4/alcohol H primary alcohol
aldehyde

In this process, NaBH4 reduces only the carbonyl group, while LiAlH4 reduces both
the carbonyl group and any unsaturated carbon atoms in the hydrocarbon chain.
H
NaBH4
CH2 CH C O CH2 CH C OH
alcohol
H H
2 – propenal 2 – propenol

H
LiAlH4
CH2 CH C O CH3 CH2 C OH
ether
H H
2 – propenal n – propanol

Addition of Water
When aldehydes react with water, unstable hydrate compounds are formed. In
this process, the hydrogen atom of water is bonded to the oxygen in the carbonyl
group and the hydroxide group of water is bonded to the carbon atom of the car-
bonyl group.
OH
d+ d– d+ d– H
+
R C O + H OH R C OH

H H
aldehyde aldehyde hydrate

74 Oxygen And Nitrogen Containing Organic Compounds

Dissolving an aldehyde in water results in the establishment of an equilibrium
between the aldehyde and its hydrate. In the aqueous solutions of low-molar
mass aldehydes, the hydrate ratio is much higher than in longer chained alde-
hyde solutions.

H H OH
C O +H OH C
H H OH
formaldehyde formaldehyde hydrate

These hydrates are unstable and can not be obtained pure.

Addition of Alcohol
Alcohols can be added to aldehydes in the presence of an anhydrous acid cat-
alyst. The alkoxide part (RO–) of the alcohol is attached to the carbon atom of
the carbonyl group of the aldehyde and the proton (H+) from the alcohol is
attached to the oxygen of the aldehyde. The new compound is called a hemiac-
etal.

OR¢
d+ d– d– d+ H
+
R C O + R¢ O H R C OH

H H
aldehyde alcohol hemiacetal

OC2H5
+
H
CH3 C O + C2H5O H CH3 C OH

H H
ethanal ethanol 1 – ethoxyethanol

Hemiacetals show properties of alcohols due to the presence of the C OH

group and react with large amounts of alcohol in the presence of an acid to pro-
duce acetal compounds which have the properties of ethers. This reaction is not
an addition reaction. All the steps in the formation of an acetal from an aldehyde
are reversible.

OR¢ OR¢
+
H
R C OH + R¢¢ OH R C OR¢¢ + H OH
alcohol
H H
hemiacetal alcohol acetal

Aldehydes and Ketones 75

 OC2H5 OC2H5
+
H
CH3 C OH + CH3 OH CH3 C OCH3 + H OH
methanol
H H
1 – ethoxyethanol ethylmethylacetal
HCN is a very harmful toxic gas. The
frightening thing is that its odor can be Acetals do not react with same reactants as aldehydes because the ether bonds
noticed only when it reaches deadly lev- in acetals give them a different structure.
els.

Addition of HCN
Addition of HCN to aldehydes produces cyanohydrins. Since HCN is a toxic gas,
–
it is not used in the reaction directly. CN salts of active metals such as Na and
K react with mineral acids such as H3PO4 and then the HCN formed reacts with
the carbonyl group.
Millipedes and HCN
Millipedes spray a toxic gas to protect While it is necessary to use an acid catalyst to react poor nucleophiles like H2O
themselves. They carry mandelanitrile and ROH with aldehydes, there is no need to use a catalyst for a strong nucle-
–
(benzaldehyde cyanohydrine) in their ophile such as CN .
protective glands. When they are
NaCN + H2SO4 NaHSO4 + HCN
attacked, cyanohydrine and an enzyme
are mixed to produce benzaldehyde CN
and HCN. This is then sprayed at the R C O +H CN R C OH
attacker. A millipede can spray enough
HCN to kill a mouse. H H
aldehyde aldehyde cyanohydrine

CN

C6H5 C O + HCN C6H5 C OH

H H
benzaldehyde benzaldehyde cyanohydrine

Addition of Grignard Reagents

Addition of Grignard reagents to aldehydes is the most important method of
preparing of alcohols. The product of these reactions is a kind of alkoxide. This
alkoxide hydrolyses in the presence of acid and forms an alcohol.

You may remember that to prepare primary alcohols by this method we should
start with formaldehyde, and to prepare secondary alcohols we should start with
higher aldehydes.
O OMgX OH
+H2O
R C H + R¢MgX R C H R C H + Mg(OH)X
aldehyde
R¢ R¢
secondary alcohol

76 Oxygen And Nitrogen Containing Organic Compounds

Addition of NaHSO3
In these reactions, the hydrogen in NaHSO3 attaches to the oxygen of the car-
–
bonyl group and NaSO3 attaches to the carbon of the carbonyl group. In this
reaction there is no need for an acid catalyst. The reaction is at equilibrium in
aqueous solution and the aldehyde can be reformed from the sodium hydrogen-
sulfite addition product by adding acid or base to the reaction mixture.
– +
SO3 Na

R C O + NaHSO3 R C OH

H H
aldehyde sodium hydrogensulfite addition product
– +
SO3 Na

H C O + NaHSO3 H C OH

H H
formaldehyde sodium formaldehyde hydrogensulfite

Generally, sodium hydrogensulfite addition products of higher molar mass alde-

hydes can be precipitated easily. Hence NaHSO3 is often used to separate alde-
hydes from mixtures.

10
Write out the addition reactions of acetaldehyde with the following substances
under suitable conditions.
a. Hydrogen, b. Water, c. Methyl alcohol, d. NaHSO3

Ni, Pt
a. CH3 C O + H2 heat and CH3 CH2 OH
pressure ethyl alcohol
H
OH
+
H
b. CH3 CH O + H2O CH3 C OH

H H
ethanal hydrate

O CH3
+
H
c. CH3 C O + CH3OH CH3 C OH

H H
methoxy ethanol
H

d. CH3 C O + NaHSO3 CH3 C OH

– +
H SO3 Na
sodium acetaldehyde
hydrogensulfite

Aldehydes and Ketones 77

 4.3. POLYMERIZATION
Aldehydes undergo polymerization reactions under certain conditions. In these
reactions, as the aldehyde molecules react with different functional groups to
form polymers.
Polymers formed when the S bonds of the aldehyde molecules open and bond to
each other are called homopolymers. Addition reactions like these are also called
parapolymerization reactions. In polymerization reactions, mineral acids are used as
catalysts and the formed product may be a ring or a linear structure.

H R
O C
O O
3R C R R or
C C
H O
H H
ring polymer

O H H H
nR C ........ C O C O C O ........
H R R R

n
linear polymer

Because aldehyde polymers do not contain aldehyde groups, they do not show
the properties of aldehydes. The boiling points of these polymers are higher than
those of the corresponding aldehydes.
Polymerization reactions of aldehydes are reversible, linear polymers being
decomposed more easily than ring polymers. Decomposition is easier under
higher temperatures and in the presence of concentrated acids.

4.4. COMBUSTION REACTION

The combustion products from the burning of aldehydes are CO2 and H2O. The
reaction is exothermic. The general combustion reaction of aldehydes is:
3n–1
CnH2nO + ––––––– O2 o nCO2 + n H2O
2
C3H6O + 4O2 o 3CO2 +3H2O

11
2.464 L of oxygen at STP is required to burn 1.44 grams of an aldehyde. What
is its molecular formula? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

78 Oxygen And Nitrogen Containing Organic Compounds

Let us find the number of moles of oxygen gas in the reaction.
2.464 L
moles of O2 = ––––––––––– = 0.11 mol
22.4 L/mol

Combustion reaction of aldehydes;

3n – 1
CnH2nO + ––––––––– O2 o nCO2 + n H2O
2
According to the equation 1 mol of aldehyde reacts with (3n–1)/2 mol O2.
Because 1 mol aldehyde is (14n + 16) g, we can find number of carbon atoms
in the aldehyde by using proportions.
3n – 1
(14n+16) g of aldehyde reacts with (–––––––––) mol of O2
2
1.44 g of aldehyde reacts with 0.11 mol of O2
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
3n – 1
0.11 (14n + 16) = 1.44 · –––––––––
2
n=4
By putting 4 into the general molecular formula, the aldehyde is found to be
C4H8O.

5. PREPARATION OF ALDEHYDES
5.1. OXIDATION OF PRIMARY ALCOHOLS
Aldehydes are readily prepared by the oxidation of alcohols. Oxidation of primary
alcohols with a catalyst produces aldehydes. Their oxidation state lies between that
of primary alcohols and that of carboxylic acids.
H H
[O]
R C OH R C O + H2O
aldehyde
H
primary alcohol

H
[O]
CH3 C OH CH3 C O + H2O

H H
ethanol ethanal

In this reaction K2Cr2O7 is used as the oxidizing agent.

Aldehydes and Ketones 79

 Condensation Reactions
Aldehydes undergo condensation reactions with different substances.
In condensations reactions, two molecules form a larger molecule.

O NOH
a. CH3 C + NH2OH CH3 C + H2O
H H
hydroxylamine ethanal oxime

O NNH2
b. CH3 C + NH2NH2 CH3 C + H2O
H H
ethanal hydrazone

12
Which alcohols need to be oxidized to produce following aldehydes?
a. Formaldehyde
b. 2 – methylpropanal
c. 2,2 – dimethylbutanal

Aldehydes are obtained by the oxidation of primary alcohols. During the oxida-
tion process, there is no change in the carbon chain of the alcohol. However, the
alcohol group is turned into an aldehyde group. According to this information:

a. There is one carbon atom in the structure of formaldehyde. So there

should be just one carbon atom in the structure of the alcohol. This is
methanol.

b. 2 – methylpropanal is obtained from 2 – methylpropanol.

c. 2,2 – dimethylbutanal is obtained from 2,2 – dimethylbutanol.

80 Oxygen And Nitrogen Containing Organic Compounds

5.2. DEHYDROGENATION OF PRIMARY ALCOHOLS If H2 is removed from a molecule, it is
called dehydrogenation. If H2 is added, it
Aldehydes are obtained from primary alcohols by removing H2 in the presence of is called hydrogenation. Hydrogenation is
a copper chromite (CuO · Cr2O3) catalyst. To do this, alcohol vapor at 250-300 °C a reduction reaction and dehydrogena-
is passed over hot CuO · Cr2O3 . One hydrogen molecule from each alcohol mol- tion is an oxidation reaction.
ecule is removed in the reaction. Thus, the alcohol is oxidized to an aldehyde. A As aldehydes are formed by the dehydro-
hydrogen molecule can also be removed from low molar mass alcohols using just genation of alcohols, their names are
derived from the first syllables (al- and
CuO as the catalyst.
dehyde-) of these words.
H H
CuO·Cr2O3
R C O 250 – 300 °C
R C O + H2
aldehyde a
H H
primary alcohol

CuO·Cr2O3
CH3CH2OH 250 – 300 °C CH3 C O + H2
ethyl alcohol H
ethanal

Heat copper foil in a bunsen burner.

Reduction of Carboxylic Acid

Just as the oxidation products of aldehydes are carboxylic acids, the reduction
products of carboxylic acids are aldehydes. To carry out this reaction, any car-
boxylic acid with formic acid is passed in gaseous state over a catalyst of TiO2 at
300-350°C. As a result, an aldehyde is obtained and CO2 and H2O are given out. It is seen that the copper foil is cov-
ered with black copper (II) oxide
O O O
(CuO)
TiO2
R C OH + H C OH 300 – 350°C
R C H + CO2 + H2O
a carboxylic acid formic acid an aldehyde c

6. SOME IMPORTANT ALDEHYDES

6.1. FORMALDEHYDE
Formaldehyde is a colorless gas with a pungent odor. It is the simplest aldehyde Hot copper oxide reacts with ethyl
and was discovered by the Russian chemist A. Butlerov in 1859. It is readily solu- alcohol, it quickly oxidizes the ethanol
to ethanal and it itself is reduced to
ble in water and it is most commonly used as a 40% solution in water known as
bright metallic copper as before.
formalin. Formaldehyde is widely used to manufacture building materials and
numerous household products. Dehydrogenation of primary alcohols

Aldehydes and Ketones 81

 Formaldehyde hardens proteins and prevents them decaying. Hence, it is used
to store biological products, to make mummies and also as a disinfectant as it
kills insects and microorganisms.

Formaldehyde exhibits most of the general chemical properties of aldehydes

though is more reactive than other aldehydes. Formaldehyde undergoes the
Cannizzaro reaction to produce formic acid and methanol.

oxidation

H H H
0 0 –2 +2
KOH
C O + C O + H2O H C OH + H C O
H H H OH
For storing biological products formalin formaldehyde formaldehyde methanol formic acid
solution, an aqueous solution of
formaldehyde 40% by mass, is used. reduction

Formaldehyde also undergoes addition, condensation, and polymerization reac-

Did you know that formaldehyde and
tions. The most interesting addition reaction of formaldehyde is the addition of
many harmful chemicals are found in
shoe polish? ammonia. In this reaction hexamethylene tetramine (urotropine) is formed. This
As a result of being exposed to shoe-pol- is used in medicine to clean urethras, in industry to harden resins and is also
ish, asthma is often found in people added to foodstuffs as a preservative.
working in shoe-shine shops. Experts
N
advise people who suffer from allergies
H H2C CH2
to polish their shoes in places such as
H2C
balconies or other well-ventilated areas. 6 C O + 4 NH3 N N
–6H2O
It should also be emphasized that these H CH2
paints should be kept out of the reach of H2C CH2
N
small children. formaldehyde hexamethylene tetramine
urotropine

Formaldehyde is easily polymerized by opening the double bond between the

carbon and oxygen atoms. When formaldehyde gas is kept at room temperature,
a white solid trimer is formed. This trimer, which has a ring structure, is known
as trioxymethylene, metaformaldehyde or trioxan.

H H
O C
O O
3H C H H
C C
H O
H H
formaldehyde trioxymethylene

This polymer dissolves in water and does not have the properties of aldehydes.
When it is needed, formaldehyde can be produced by heating trioxymethylene.

82 Oxygen And Nitrogen Containing Organic Compounds

When formaldehyde is heated, a white crystalline polymer that melts at 123 °C is
a
obtained. This polymer, known as paraformaldehyde, is formed from between 50
to 100 monomers of formaldehyde. It is a linear polymer and decays into formalde-
hyde when heated.

O H H H
nH C ........ C O C O C O ........
H H H H
formaldehyde paraformaldehyde

When formaldehyde is heated with concentrated sulphuric acid, it forms the poly-
Dilute HCl is poured into a solution of
mer polyoxymethylene, which contains at least 100 monomers. Polyoxymethylene formaldehyde, acetic acid and phenol.
is linear like paraformaldehyde. The main difference between the two of them is the
b
number of monomers in the polymer. When heated, it also decays into formalde-
hyde. It is widely used in the textile industry.

Formaldehyde is obtained by the oxidation of methyl alcohol. In the laboratory,

acidic solutions of KMnO4, K2Cr2O7 or K2CrO4 can be used as the oxidizing agent.

5CH3OH + 2KMnO4 + 3H2SO4 o 5HCHO + K2SO4 + 2MnSO4 + 8H2O

The bitter, stinging smell of the produced formaldehyde is observed during the
reaction.

In industry, formaldehyde is obtained by heating a methanol and air mixture. This

When the mixture is stirred it heats up
reaction is the dehydrogenation of methanol (Hoffman method). The process is and its color turns pink. This indicates
carried out by using the oxygen from the air with a catalyst of copper and silver. that the polymer is forming.

250 °C c
Cu + 1/2 O2 CuO

CuO + CH3OH H C O + Cu + H2O

H
Cu
CH3OH + 1/2 O2 H C O + H2O
250 °C

H
methyl alcohol formaldehyde

6.2. ACETALDEHYDE As a result of stirring the solution for

one minute, solid phenolformaldehyde,
Pure acetaldehyde is a colorless, volatile and poisonous liquid that is miscible a condensation polymer is formed.
with water. The boiling point of acetaldehyde is 21 °C. This polymer can be pulled from the
mixture with the stirring rod.
Acetaldehyde is used for synthesizing of many organic compounds such as
acetic acid, ethyl alcohol and synthetic rubber. Formation of a polymer

Aldehydes and Ketones 83

 Cu
CH3 C O + 1/2 O2 CH3 C O
250°C

O H OH
CH3 C
acetaldehyde acetic acid
H
acetaldehyde Pt – Ni
CH3 C O + H2 CH3 CH2 OH
200°C
ethyl alcohol
H
acetaldehyde

Acetaldehyde undergoes polymerization reactions similar to formaldehyde.

Acetaldehyde reacts with itself in the presence of H2SO4 at room temperature to
form paraldehyde, a trimer, though at 0 °C it forms methaldehyde, a tetramer.

H CH3
O C
Do you know?! O O
Acetaldehyde is an air pollutant emit- 3 CH3 C H3C H
C C
ted by cars and certain production H O
H CH3
facilities. It is also contained in tobacco
smoke. acetaldehyde paraldehyde

It is classified as a probable carcinogen.

Paraldehyde, which boils at 124 °C, has a pleasant fruity smell. It causes people
to feel sleepy, and is hence used for hypnosis in medical science. It changes back
to acetaldehyde when boiled with dilute H2SO4 .

Methaldehyde is a solid that sublimes at 112 °C. It was given to soldiers in World
War I to heat their meals under the name of solid ethyl alcohol.

H CH3
H O C
O
H2SO4 C O
4 CH3 C H3C H
O C
H
acetaldehyde C O CH3
H CH3
methaldehyde

Acetaldehyde forms resins when boiled in strong concentrated basic solutions.

Many acetaldehyde molecules attach together to form a linear polymer.

O H H H
n CH3 C ........ C O C O C O ........
H CH3 CH3 CH3
acetaldehyde
polyoxyethylene

84 Oxygen And Nitrogen Containing Organic Compounds

7. KETONES
Compounds with two alkyl groups or aryl groups attached to the carbonyl group O O
are known as ketones.
R C R R C R¢
The general molecular formula of ketones is CnH2nO. So aldehydes and ketones a simple ketone a mixed ketone
symmetrical ketone unsymmetrical ketone
having same number of carbon are structural isomers of each other.

8. NOMENCLATURE OF KETONES
8.1. COMMON NAMES
Common names use the names of the R (alkyl groups) or Ar (Arene group) as
separate words, along with word ketone.
O O O

H3C C CH3 H3C C CH2 CH3 C CH3

dimethyl ketone ethyl methyl ketone methyl phenyl ketone

13
Name the following compounds.
O CH3 O CH3

a. CH3 CH2 C CH CH3 c. CH3 C C CH3

CH3

O O

b. C CH2 d. C CH CH3

CH3

a. Ethyl isopropyl ketone b. Benzyl phenyl ketone

c. Methyl tertiary butyl ketone d. Phenyl isopropyl ketone

8.2. USING THE IUPAC SYSTEM

The longest carbon chain containing the carbonyl group is selected and num-
bered starting with the carbon atom nearest the carbonyl group. If substitutents
are present on the main chain, they are indicated by number of the carbon atoms
to which they are attached. The number of the carbon atom of the carbonyl
group is added to the front of the ketone. The IUPAC system replaces the –e of
the name of the corresponding alkane by the suffix –one.

Aldehydes and Ketones 85

 O O O CH3
1 2 3 4 5 5 4 3 2 1
H3C C CH3 H3C C CH2 CH2 CH3 H3C CH2 C C CH3
propanone 2 – pentanone CH3
2,2 dimethyl 3 – pentanone

14
What are the IUPAC names of the following compounds?
O CH3 O O
H3C
a. H3C C CH CH3 b. O c. CH3 C C CH3

CH3

d. H3C C C CH3 e. CH3 f. CH3 CH2 CH2

O
C O
O CH3
H3C

O Cl O
g. H3C CH C CH2 h. H3C C C CH2 CH3
Br Cl

a. 3 – methyl – 2 – butanone
b. 3 – methyl cyclopentanone
c. 2,3 – butadione
d. 3,3 – dimethyl – 2 – butanone
e. 3 – methyl cyclohexanone
f. 2 – pentanone
g. 1 – phenyl – 3 – bromo – 2 – butanone
h. 2,2 – dichloro – 3 – pentanone

9. PHYSICAL PROPERTIES OF KETONES

Low molar mass ketones are liquids. Ketones with more than C11 atoms are
solids. Liquid ketones readily dissolve in water as they form hydrogen bonds with
water molecules. Liquid ketones are used as solvents in the preparation of paint
chemicals. Solubility of ketones decreases with increasing size of the molecule.
Ketones, compared to aldehydes, have more pleasant odor.

86 Oxygen And Nitrogen Containing Organic Compounds

Ketones are polar molecules because of the carbonyl group, but there is no hydro-
gen bonding between the molecules. The polarity of ketones decreases with
increasing size of the groups attached to the carbonyl group. The polarity of
ketones is much greater than that of ethers, hence ketones boil at higher temper-
atures than hydrocarbons and ethers with similar molar masses but boil at lower
temperatures than corresponding alcohols.

CH3 O OH

Formula : H3C CH CH3 H3C O C2H5 H3C C CH3 H3C CH CH3

Name : isobutane ethyl methyl ether dimethyl ketone isopropanol
Boiling point : – 12 °C 10.8 °C 56 °C 82.3 °C

Melting Boiling *Solubility in

*Density Water (g/100 mL
Name Structure Point Point
(g/mL) H2O)
(°C) (°C)

Acetone CH3COCH3 – 95 56 0.790 f

2 – Butanone CH3COCH2CH3 – 86 80 0.805 very soluble
2 – Pentanone CH3COCH2CH2CH3 – 78 102 0.812 soluble
3 – Pentanone CH3CH2COCH2CH3 – 39 102 0.816 soluble
2 – Hexanone CH3CO(CH2)3CH3 – 57 127 0.830 slightly soluble
Acetophenone CH3COC6H5 21 202 1.028 insoluble
Benzophenone C6H5COC6H5 48 306 1.100 insoluble

* The values are given for 20°C.

Table 2: Some ketones and their physical properties.

15
Arrange the following compounds, all with the general formula (C4H8O), in order
of decreasing boiling point.

I. CH3 C C2H5 II. CH3CH2CH2CH2 OH

III. CH2 CHCH2CH2 OH IV. CH2 CH O CH2CH3

Compound I is a ketone, II is a primary alcohol, III is a primary alcohol of alkene

derivation and IV is an ether derivative.
So the order of decreasing boiling points are II, III, I and IV.

Aldehydes and Ketones 87

 10. CHEMICAL PROPERTIES OF KETONES
Since ketones do not have a hydrogen atom directly bonded to their carbonyl
group they don't behave as reducing agents like aldehydes. They are rather
resistant towards oxidation and can be used for many oxidation reactions as sol-
vents. However, when they are heated with very strong oxidizing agents for a long
time, their carbon chains are broken. As a result, the ketone is either oxidized to
a carboxylic acid or is decomposed. Ketones do not react with Tollens', Fehling's
or Benedict's reagents. Under specific conditions, symmetric ketones may be
oxidized to two different carboxylic acids, and unsymmetric ketones oxidized to
four different acids.

O
KMnO4/H2SO4
CH3 C CH3 CH3 COOH + H COOH
heat
acetone acetic acid formic acid

O
KMnO4/H2SO4
2CH3 C C3H7 heat
CH3COOH + HCOOH + C2H5COOH + C3H7COOH
2–pentanone acetic acid formic acid propionic acid butyric acid

Carbon and oxygen atoms become active by the breaking of the S bond in the
ketone carbonyl group. Even though ketones are less reactive than aldehydes,
they undergo all the same addition reactions as aldehydes.

10.1. ADDITION REACTIONS

Addition of Hydrogen (Reduction of Ketones)

Hydrogen can be added to ketones using metal catalysts such as Ni, Pt and Pd
to form secondary alcohols. In these reactions, the ketones are reduced.

O OH
Ni
R C R¢ + H2 heat, pressure
R C R¢
ketone
H
secondary alcohol

Addition of Water
By adding water to ketones, unstable ketone hydrates are formed. In this
process, the hydrogen of water attaches to the oxygen of the carbonyl group and
the hydroxyl group of water attaches to the carbon of the carbonyl group.

Ketone hydrates and ketones are in equilibrium in aqueous solution.

88 Oxygen And Nitrogen Containing Organic Compounds

 OH
+
H
R C O + H OH R C OH

R¢ R¢
ketone ketone hydrate

Addition of Alcohol
Alcohols can be added to ketones in the presence of anhydrous acids. In the
reaction, the alkoxide part of the alcohol (RO–) is attached to the carbon of the
carbonyl group and the proton from the alcohol (H+) is attached to the oxygen
of the ketone.

O R¢¢
+
H
R C O + R¢¢ OH R C OH
alcohol
R¢ R¢
ketone hemiketal

Ketones form hemiketals upon reaction with alcohols. Because of the COH
group, hemiketal compounds display the properties of alcohols and can react fur-
ther with alcohols to form ketal compounds which have the properties of ethers.
OR¢¢ OR¢¢
H+
R C OH + R¢¢ OH R C OR¢¢ + H OH
alcohol water
R¢ R¢
hemiketal ketal

Addition of HCN
Ketones form cyanohydrin compounds upon the addition of HCN. Since HCN is
a toxic gas, it is not used directly in the reactions, instead, the NaCN salt is treat-
ed with a mineral acid (such as H2SO4).

NaCN + H2SO4 NaHSO4 + HCN

CN

R C O +H CN R C OH

R R
ketone ketone cyanohydrin

CN

H3C C O + HCN H3C C OH

CH3 CH3
acetone acetone cyanohydrin

Aldehydes and Ketones 89

 Ketones having large groups attached to the carbonyl group do not undergo
addition reactions with HCN.

Addition of Grignard Reagents

Addition of Grignard reagents (RMgX) to ketones is one of the most important
preparation methods of alcohols. The addition products hydrolyse in the pres-
ence of an acid to form tertiary alcohols.

OMgX OH
+HOH
R C O + R¢¢MgX R C R¢¢ R C R¢¢ + Mg(OH)X

R¢ R¢ R¢
ketone Grignard addition tertiary
compound alcohol

OMgI OH
+HOH
CH3 C O + CH3MgI CH3 C CH3 CH3 C CH3
–Mg(OH)I

C2H5 C2H5 C2H5

2 - butanone Grignard addition 2 methyl - 2 - butanol
compound

Addition of NaHSO3
Ketones, apart from acetone and aromatic ketones, do not react with NaHSO3 .
In the addition process of the ketones that do react, hydrogen from NaHSO3
–
attaches to the oxygen of the carbonyl group and NaSO3 attaches to the carbon
of the carbonyl group. The product is a crystalline solid. In this reaction, there is
no need for a catalyst.
– +
SO3 Na

R C O + NaHSO3 R C OH

R¢ R¢
ketone

– +
SO3 Na

CH3 C O + NaHSO3 CH3 C OH

CH3 CH3
acetone

NaHSO3 is used to separate ketone compounds, especially acetone, from mix-

tures.

90 Oxygen And Nitrogen Containing Organic Compounds

 16
Assuming suitable conditions, write out the addition reactions of dimethyl ketone
with following substances.
a. Hydrogen b. Water
c. Methyl alcohol d. HCN
e. CH3MgCl/H2O f. NaHSO3

Ni
a. CH3 C O + H2 heat, pressure
CH3 CH CH3

CH3 OH

OH
+
H
b. CH3 C O + H 2O CH3 C OH

CH3 CH3

OCH3

c. CH3 C O + CH3OH CH3 C OH

CH3 CH3

CN
d. CH3 C O + HCN CH3 C OH

CH3 CH3

OMgCl OH
+HOH
e. CH3 C O + CH3MgCl CH3 C CH3 CH3 C CH3
–MgOHCl
CH3 CH3 CH3

– +
SO3 Na

f. CH3 C O + NaHSO3 CH3 C OH

CH3 CH3

17
What is the molecular formula of the alcohol obtained by adding 2.8 L H2 at STP
with 9 grams of ketone? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

Aldehydes and Ketones 91

 2.8 L
Number of mol H2 Ÿ n = ––––––––––– = 0.125 mol.
22.4 L/mol
Ketones undergo an addition reaction with H2 gas according to the following
equation.
R C O + H2 R CH OH

R R

According to the equation, 1 mol H2 reacts with 1 mol ketone. So, 0.125 mol H2
reacts with 0.125 mol ketone.
0.125 mol ketone is 9g
1 mol ketone is xg
–––––––––––––––––––––––––––––––––––
x = 72 g
The molar mass of the ketone is 72 g/mol. And, according to reaction given
above molar mass of alcohol must be 74 (molar mass of ketone and hydrogen)
As we know that (–CH–OH) group in alcohol has 30 grams mass, then,
74 – 30 = 44 grams must be total mass of the remaining part of alcohol.
Consequently, the molecular formula of the alcohol is
CH3 CH2 CH OH

CH3

18
Which ketone should be used to prepare tertiary butanol by the addition of a
Grignard Reagent?

The molecular formula of tertiary Ketones have 2 alkyl groups and at

butanol is least 3 carbon atoms, in the struc-
CH3 ture of a Grignard reagent, there is 1
alkyl group. So, the Grignard
CH3 C OH
reagent must be CH3MgX and the
CH3 ketone
CH3 C CH3

92 Oxygen And Nitrogen Containing Organic Compounds

 19
What is the molecular formula of a simple ketone if 0.2 mole of the product that
is produced by the reaction of this ketone with HCN weighs 22.6 grams?

Addition of HCN to ketones occurs according to the following equation.

CN

R C O + HCN R C OH

R R

Let us find the molar mass of the product.

0.2 mol compound 22.6 g
1 mol compound xg
–––––––––––––––––––––––––––––––––––––––––––––––
x = 113 g
Since the molar mass of the compound R(Rc)C(CN)OH is 113 g/mol, 55 g/mol
of this belongs to the ( C(CN)OH) group and 113 – 55 = 58 g/mol belongs to
the alkyl groups.
Because the ketone is symmetrical, the alkyl groups are the same. So, the molar
mass of one alkyl group is 58 g/mol / 2 = 29 g/mol. So, the alkyl group is C2H5
and the molecular formula of the ketone is C2H5 C O
C2H5

20
What is the molar mass of the ketone of which 0.2 mole of its addition product
with sodium hydrogensulfite weighs 35.2 grams?
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol, S : 32 g/mol, Na : 23 g/mol)

Addition of sodium bisulfite to a ketone occurs according to the following equa-

tion.
SO3Na

R C O + NaHSO3 R C OH

R R

The number of moles of product equals that of the ketone. So the molar mass
of the product can be calculated.

Aldehydes and Ketones 93

 M = 35.2 g / 0.2 mol = 176 g/mol.
R
C(SO3Na)OH
R

In this compound, the molar mass of the (SO3Na) OH group is

M = S + (3 . O) + Na + O + H = 32 + (3 . 16) + 23 + 16 + 1 = 120 g/mol

Consequently, the molar mass of the R C group is 176 – 120 = 56 g/mol

R
Therefore the molar mass of the ketone R C O is

56 + 16 = 72 g/mol. R

21
A 1 mole of acetaldehyde and acetone undergoes an addition reaction with an
excess amount of methanol to form 97 grams of addition product.
According to this information, what is the mass of acetone in the initial mixture?
(C4H10O2 : 90 g/mol)

The mixture of acetaldehyde - acetone reacts with methanol as follows:

O CH3

CH3 C O + 2CH3OH CH3 C O CH3 (I)

–H2O
H H
acetaldehyde
O CH3

CH3 C O + 2CH3OH CH3 C O CH3 (II)

–H2O
CH3 CH3
acetone

At the beginning, if there is x mole of acetaldehyde there is, (1 - x) mole of ace-

tone.

According to the first equation, 1 mole of acetaldehyde produces 1 mole of prod-

uct, so x mole of acetaldehyde produces x mole of product. The molar mass of
the formed 1,1 - dimethoxyethane is 90 g/mol.

and the mass of the compound is m = n . M = 90 x g

According to the second equation, 1 mole of acetone produces 1 mole of ketal

compound, so (1 - x) mole of acetone produces (1 - x) mole of ketal compound.

94 Oxygen And Nitrogen Containing Organic Compounds

The molar mass of the ketal compound is
MC = (5 . 12) + (1 . 12) + (2 . 16) = 104 g/mol
5H12O2
and the mass of the compound is
m = n . M = (1 – x) . 104 g
The sum of the mass of these two compounds should be 97 grams.
90x + [(1 – x) . 84] = 97
x = 0.5 mol
In 1 mole of mixture, there is 0.5 mol of acetaldehyde and 1 – 0.5 = 0.5 mol of
acetone. According to this, the mass of acetone in the mixture is
m = n . M = 0.5 mol . 58 g/mol = 29 g

10.2. COMBUSTION REACTION

Combustion reaction of ketones are exothermic. General combustion reaction of
ketones occur according to the following equation.
3n–1
CnH2nO + ––––––– O2 o nCO2 + n H2O
2
C3H6O + 4O2 o 3CO2 +3H2O

11. PREPARATION OF KETONES

11.1. OXIDATION OF SECONDARY ALCOHOLS
Ketones are formed by oxidising secondary alcohols. The boiling points of
ketones are lower than those of the corresponding alcohols. As mentioned pre-
viously, oxidation can occur with different reactants under different conditions.
H
[O]
R C OH R C O + H2O

R R
secondary alcohol ketone

H
[O]
CH3 C OH CH3 C O + H2 O

C2H5 C2H5
secondary butanol butanone

Aldehydes and Ketones 95

 11.2. DEHYDROGENATION OF SECONDARY ALCOHOLS
One hydrogen molecule and a ketone are formed when secondary alcohols in
the vapor state are passed over CuO · Cr2O3 granules.
H H
CuO . Cr2O3
R C O R C O + H2
250 °C
R¢ R¢
secondary ketone
alcohol

H H
CuO·Cr2O3
CH3 C O H3C C O + H2
250 °C
C3 H7 C3H7
2 – pentanol 2 – pentanone

11.3. HEATING CALCIUM SALTS OF CARBOXYLIC ACID

The dry distillation of the calcium salts of carboxylic acids produces ketones.
R
heat
Ca(R COO)2 C O + CaCO3
calcium R
carboxylate
ketone
H3C
heat
Ca(CH3COO)2 C O + CaCO3
calcium acetate H3C
acetone

11.4. ADDITION OF WATER TO ALKYNES

By adding of water to alkynes other than acetylene, ketones are produced. The
addition reaction occurs in the presence of H2SO4 and HgSO4 catalysts.
H
H+
R C C H+H OH R C C H R C C H
HgSO4
alkyne
OH H O H
enol ketone
(enol structure) (keto structure)

H+
CH3 C C H+H OH CH3 C C H CH3 C CH3
HgSO4
propyne
OH H O
propen–2–ol propanone
(acetone)

96 Oxygen And Nitrogen Containing Organic Compounds

12. ACETONE
Acetone, also called propanone or dimethyl ketone, is the smallest ketone. It is The most familiar household use of ace-
a colorless, volatile liquid with a pleasant odor. The boiling point of acetone is tone is as the active substance in nail
56 °C. It can mix with water, alcohol and ether in all proportions. It is a wonder- polish remover.
ful organic solvent, dissolving varnishes, lacquers, resins, plastics, paints, oils
and their derivatives.

A large amount of acetone is present in people who suffer from diabetes and
consequently their urine contains a considerable amount of acetone. Hence the
urine of diabetes sufferers will give off a distinctive acetone odor.

Acetone burns with a blue dull flame. It is very difficult to oxidize, though possi-
ble when reacted with strong oxidizing agents. Acetone is different to other
ketones in that it may be polymerized.

12.1. PREPARATION OF ACETONE

Distillation of Wood
The distillation product of wood contains 0.5% acetone. It may be isolated by
fractional distillation.

Heating of Calcium Acetate

Acetone is obtained from the dry heating of the calcium acetate salt. However, calcium
acetate
the yield of the reaction is low. ice

H3C COO O
acetone
heat
Ca H3C C CH3 + CaCO3
acetone
H3C COO
calcium acetate

Oxidation of Isopropyl Alcohol Preparation of acetone from calcium

Acetone is obtained from the oxidation of isopropyl alcohol, a secondary alcohol. acetate.
Oxidation occurs with oxidizing agents such as acidified KMnO4 solution.

OH O

5 CH3 CH CH3 + 2KMnO4 + 3H2SO4 5 H3C C CH3 + K2SO4 + 2MnSO4+ 8H2O

isopropyl alcohol acetone
In addition, acetone may be obtained by the reaction of isopropyl alcohol vapor
with air at high temperatures in the presence of Cu and Ag catalysts.
OH O
Cu(300 – 400 °C)
CH3 CH CH3 + 1/2O2(air) –H2O
CH3 C CH3
isopropyl alcohol acetone

Aldehydes and Ketones 97

 From Acetic Acid
Preparation of acetone in high yields can be achieved by passing acetic acid
vapor over a metal oxide catalyst such as MgO, CaO or Al2O3 .
–
CH3COO
+2
2CH3COOH + MgO Mg + H2O
–
CH3COO
acetic acid magnesium acetate

– O
CH3COO
+2 heat
Mg CH3 C CH3 + MgCO3 (MgO + CO2)
– acetone
CH3COO
magnesium acetate

22
A formaldehyde-acetone mixture contains 80% acetone by mass. When this mix-
ture reacts with Fehling's reagent, 14.3 gram of solid Cu2O is produced.
What is the total mass of the mixture?
(C : 12g/mol, H : 1 g/ mol, O : 16 g/mol, Cu : 63.5 g/mol)

When an acetone - formaldehyde mixture reacts with Fehling's reagent, acetone

does not participate. However, formaldehyde reacts according to the following
equation.
HCHO + 2Cu+2 + 4OH– o HCOOH + Cu2O + 2H2O
MCu2O : (2 . 63.5) + 16 = 143 g/mol
MHCHO : (2 . 1) + 12 + 16 = 30 g/mol
According to the equation, 30 grams of formaldehyde forms 143 grams of Cu2O.
The mass of formaldehyde in the mixture is found by the proportion method.
143 grams Cu2O is produced from 30 grams of HCHO
14.3 grams Cu2O is produced from x gram HCHO
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
x=3g
If 80% of mixture is acetone, 20% of mixture is formaldehyde, 20% of formalde-
hyde is 3 grams.
20% mixture 3 grams
100% mixture x grams
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
x = 15 grams
So the mass of the mixture must be 15 grams.

98 Oxygen And Nitrogen Containing Organic Compounds

1. Name the following compounds. 4. Give the molecular formulae for the following com-
O O
pounds.
a. 3 – penten – 2 – al
a. CH3 CH C d. C
b. 2 – methylbutanal
CH3 H H
c. 4 – nitrobenzaldehyde
O O d. 3,3,3 – trichloropropanal
b. CH3 CH C e. CH3 CH CH2 C e. 2,3 – dihydroxyhexanal
CI H CH3 H f. 4–bromo–2–methylpentanal

Cl O O
c. CH3 C CH2 C f. CH3 (CH2)6 C
5. Write down the molecular formulae of aldehydes con-
Cl H H
taining.
a. 1 carbon atom
b. 2 carbon atom
c. 3 carbon atom
Give the common and IUPAC names of these com-
2. Give the IUPAC names of the following compounds. pounds.
CH3 O CH3 O
a. C CH2 C d. CH3 C C

CH3 H CH3 H 6. Draw the structural formulae of the aldehyde com-

pounds having the following molecular formulae.
O O a. C4H8O b. C5H8O c. C5H10O
b. CH2 CH CH2 C e. CH2 (CH2)4 C

OH OH H CN H

O O O 7. The compounds given below first react with C2H5MgBr

c. CH2 C CH C f. C (CH2)2 C and then with HBr. Give the molecular formulae and the
H H H names of the products.
Br CH3
a. H C O b. CH3 C O

H H

c. C O d. CH3 CH C O
3. Draw the structural formulae of the following com- H CH3 H
pounds, their common names are given.
a. Propionaldehyde
b. Isobutyraldehyde
c. E – hydroxyvaleraldehyde 8. Which aldehydes are obtained when the following alco-
d. Phenylacetaldehyde hols are oxidized?
e. D – bromobutyraldehyde a. Ethyl alcohol b. Neopentyl alcohol
f. o – hydroxybenzaldehyde c. 2 – methylbutanol d. Isobutyl alcohol

Aldehydes and Ketones 99

9. When 1 gram of a mixture of formaldehyde - formic acid 16. When 0.2 mol of an aldehyde is oxidized, 14.8 gram of a
reacts with Tollens' reagent, Ag+ ions are reduced to Ag carboxylic acid is formed. What is the molecular formula
(metallic silver). In total, 5.4 grams of Ag metal are of the aldehyde and its molar mass?
formed. What are the mass percentage of formic acid in
the mixture?
17. What is the molecular formula and the mass of the alde-
hyde that is formed from the oxidation of 18.4 gram,
10. When 15 grams of a monoalcohol is oxidized, 5.6 L of 80% ethyl alcohol?
gaseous aldehyde is obtained at STP. What is the molar
mass of this aldehyde?
18. Starting from aldehydes and by choosing appropriate
reagents, show by using equations how the following
11. What is the molecular formula of the aldehyde that con- compounds could be obtained?
tains 69.77% C, 11.63% H and 18.60% O by mass? a. Ethyl alcohol e. Acetaldehyde hydrate
b. Acetic acid f. Acetaldehyde cyanohydrine
12. Which functional groups does the c. Ethoxyethanal g. Trichloroethanal
H
compound vanillin, shown on the right, d. Propanoic acid
C O
contain?

19. Write equations for the following reactions.

OCH3 a. n – butanal + hydrogen
OH b. Isobutanal + ethanol
c. Acetaldehyde + methanol
13. Compare the boiling points of liquids given below. d. Neopentanal + water
Explain.
A B C
20. 40.4 gram of 1,2 - dibromopropane is treated with dilute
KOH solution. The product reacts with H2O and is then
oxidized. What is the mass of the substance that is
formed at the end of the reaction?
Ethyl alcohol Dimethyl ether Acetaldehyde
C2H5OH CH3OCH3 CH3CHO (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol, Br : 80 g/mol)

14. Compare the following compounds with respect to their 21. Ethylene dibromide,
solubilities in water. a. Is first heated with dilute NaOH solution and it turned
I. n – propanol into an alcohol. What is the molecular formula of this
II. n – propanal alcohol?
b. Then, the alcohol is oxidized once by KMnO4. What is
III. n – butane
the molecular formula of the aldehyde produced and
IV. Methoxyethane
find its molar mass?

15. I. Acetylene
22. I. X + NaOH Y + NaBr
II. Acetylene chloride
III. Ethyl alcohol O
K2Cr2O7/H +
IV. Isopropanol II. Y CH3 C

In which of the above compounds could an addition H

product be an aldehyde? What are X and Y in the reactions above?

100 Oxygen And Nitrogen Containing Organic Compounds

23. Starting from 0.25 mole of CaC2 how many grams of an O
aldehyde can be produced? Show with equations. e. C

24. Acetaldehyde, acetone and ethanol are present in three

different containers. Explain in detail how you could
determine which compound was in which container.
29. Complete and balance the following equations.
25. Using CaC2, H2, H2O and acidic K2Cr2O7 solution; CuO, Cr2O2
a. CH3 CH CH3 heat
write out the synthesis reactions for these compounds. OH
I. Acetylene K2Cr2O7/H+
b. CH3 CH CH3 heat
II. Acetaldehyde
OH
III. Ethyl alcohol O
IV. Acetic acid Pt
c. CH3 CH2 C CH3 + H2 heat

d. CH3 CH2 C O + H2O

26. Water vapor is reacted with acetylene gas in the pres-
ence of a HgSO4 catalyst. H

a. What is the name and the molecular formula of the

compound produced?
30. How many structures of ketones with the molecular for-
b. If 16.8 L of acetylene is used at STP in a reaction of mula C5H10O can be written? Draw them.
75% efficiency, what mass of compound is formed?

O
27. When CH2 C (hydroxyethanal) is reacted with a 31. For acetone
H a. Write its molecular formula
OH
b. Give its lUPAC name
large amount of acidic KMnO4 , what is the molecular
c. Identify any aldehydes and ketones that are isomers
formula and the molar mass of the new compound?
of acetone.

28. Name the following compounds.

32. Which of the given compounds are aldehydes (if any)
H3C O
and why?
a. CH C CH3
a. CH3 CH OCH3
H 3C
O OCH3

b. CH3 CH CH2 C CH3 O

b. O
OH

O
c. O
c. C CH2 OH
O

d. CH2 C C CH CH2 d. O C CH2 CH CH2 C O

C2H5 H OH H

Aldehydes and Ketones 101

1. CH3 CH2 CH CH C O 3. I. CH3OH
CH3 CH3 H II. H C O

H
The above compound is correctly named by which of
III. CH4
the following?

A) 2,4 – dimethylpentanal Compare the compounds above with respect to their

boiling points.
B) 2,3 – dimethylpentanal
C) 2,3 – dimethyl – 1 – pentanol A) I > II > III B) III > II > I C) I = II = III
D) 3 – ethyl – 2 – methyl – 1– butanal D) II > I > III E) III > I > II
E) n – heptanal

+ – –
4. CH3CHO + 2Ag + 3OH o 2Ag + CH3COO + 2H2O
According to this equation, how many grams of metallic
silver precipitates when 0.22 gram of CH3CHO is react-
ed?
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol, Ag : 108 g/mol)
2. Which of the following aldehydes are named incorrectly?
A) 0.54 B) 1.08 C) 1.62 D) 2.16 E) 4.32
I. CH3 CH C O

CH3 H
n – butanal
CH3

II. CH3 CH2 C CH2 C O

CH3 H
3,3 dimethylpentanal
5. CH3 CH C O
III. CH2 CH2 C O CH3 H
H This compound,
3 – phenylpropanal
I. is named as 2 – methylpropanal.
IV. CH3 CH CH CH CH C O
II. reacts with Na metal.
OH OH OH OH H III. reacts with Tollens' reagent.
2,3,4.5 – tetrahydroxyhexanal
Which of the statements above is(are) true?

A) I only B) II only C) III only A) I only B) II only C) I and III

D) I and III E) II and IV D) I and II E) I, II and III

102 Oxygen And Nitrogen Containing Organic Compounds

6. CH3 CH CH C O 9. Which one of the following compounds produces
2 – methyl – 3 – pentanone when it is partially oxidized?
OH CH3 H
For the above compound, A) 2 – methyl – 3 – pentanol
I. When it reacts with Na, H2 gas is evolved B) 2 – hydroxyhexane
C) 2 – methyl – 2 – hydroxypentane
II. When it reacts with silver nitrate and ammonia, metal-
lic silver precipitates. D) 3 – methyl – 2 – hydroxypentanol
III. It undergoes an addition reaction with H2 . E) n – hexanol

Which of the statements above is(are) true?

A) I only B) I and II C) II and III

D) I and III E) I, II and III 10. CH3 CH2 C CH3

O
I. Ethyl methyl ketone
II. 2 – butanone
III. Buten – 2 – one
Which of the names above describe the compound cor-
rectly?
+ +
7. RCHO + 2Ag + H2O o RCOOH + 2Ag + 2H
A) I only B) I and II C) II and III
According to the equation above, 5.8 grams of aldehyde
RCHO produces 21.6 grams of metallic silver. Which D) I and III E) I, II and III
one of the following is the molecular formula of this
aldehyde ?
(Ag : 108 g/mol, H : 1 g/mol, O : 16 g/mol)
11. (R COO)2Ca R C R + CaCO3
A) H C O B) CH3 C O
O
H H
In the reaction above, 15.8 gram of (RCOO)2Ca pro-
C) C2H5 C O D) C3H7 C O duces 10 grams of CaCO3 .

H H How many C atoms are there in the structure of the pro-

duced ketone?
E) C4H9 C O (Ca : 40 g/mol, C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)
H A) 3 B) 4 C) 5 D) 6 E) 7

12. I. Methanal
II. Ethanal
III. Propanal
Which of the compounds above do not have a ketone
8. Which one of the following compounds reduces the Ag+
isomer?
ion in silver nitrate and ammonia solution?
A) II only B) III only C) I and II
A) Aldehyde B) Ketone C) Alkene
D) Carboxylic acid E) Ester D) II and III E) I, II and III

Aldehydes and Ketones 103

13. I. H C O 17. Aldehydes,
I. can be oxidized.
H
II. can be reduced.
II. CH3 C O
III. can produce polymers.
CH3 Which of the statements above is(are) true?
III. CH3 C O
A) I only B) II only C) III only
H D) I and III E) I, II and III
Which of the above compounds can not be oxidized?

A) I only B) II only C) III only

D) II and III E) I and III
18. Which one of the following is not a property of ketones?

A) They can be reduced.

B) They can be oxidized.
14. I. CH3 C O C) They undergo addition reactions.
D) The can be polymerized.
H
E) Combustion products are CO2 and H2O.
II. CH3 C CH

III. CH3 CH C O

OH H
Which of the compounds above precipitate metallic sil- 19. Some compounds have more than one name. Pairs of
ver when reacted with AgNO3 in ammonia solution? names are given below.

A) I only B) III only C) I and III I. Dimethyl ketone, acetone

D) II and III E) I, II and III II. Methanal, formaldehyde
III. Ethanal, acetaldehyde
Which pairings represent the same compound?
A) I only B) II only C) I and II
15. I. Undergo reduction to form primary alcohols. D) II and III E) I, II and III
II. React with Fehling's reagent
III. When they burn, CO2 and H2O are formed
Which of the properties above apply to ketones?

A) I only B) III only C) I and III 20. 3 methyl and an aldehyde group are attached to a car-
bon atom.
D) II and III E) I, II and III
I. 2,2 – dimethylpropanal
II. Isopentanal
III. n – pentanal
16. Which one of the following is formed when isopropyl Which of the names above represent this compound
alcohol is partially oxidized? correctly?

A) Propanol B) Dimethyl ether C) Acetone A) I only B) I and II C) III only

D) Ethyl methyl ketone E) Propanoic acid D) I and III E) I, II and III

104 Oxygen And Nitrogen Containing Organic Compounds

 –
21. Which one of the following compounds forms acetone 25. CH3CHO + 2Cu+2 + 5OH o
when it is partially oxidized? –
Cu2O + CH3COO + 3H2O
A) CH3 CH2 C O B) CH3CH2 COOH According to the above equation, how many grams of
acetaldehyde are needed to precipitate 28.8 grams
OCH3 of Cu2O?
C) COOH D) CH3
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol, Cu : 64 g/mol)
CH OH CH OH
A) 1.53 B) 9.2 C) 8.8 D) 2.35 E) 1.27
COOH CH3

E) CH2 OH

CH2

CH2 OH

26. I. OH II. OH

CH3 C H CH3 C H

H CH3
22. I. 1 – butanol
II. 2 – butanol III. OH
III. 2 – methylpropanol CH3 C CH3
Which of the given alcohols form a ketone when oxi-
H C CH3
dized?
OH
A) I only B) II only C) III only
D) I and II E) II and III Which of the above alcohols produce a ketone when oxi-
dized?

A) I only B) II only C) III only

D) I and II E) II and III
23. The following statements describe formaldehyde,
I. When it polymerizes with phenol, bakelite is
obtained.
II. When it reacts with ammonia, hexamethylene
tetramine (urotropine) is formed.
III. When it is partially oxidized, formic acid is formed.
27. For
Which are true?
O O
A) I only B) II only C) I and II C and C
D) II and III E) I, II and III CH3 C2H5
C3 H 7 C2H5

I. They are isomers of each other.

II. They are isomers of 3 – methyl – 1– butanol.
24. To reduce 2.2 grams of acetaldehyde, how many liters of III. They undergo an addition reaction with NH3 .
H2 are needed at STP? Which of the above statements is (are) true?
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)
A) I only B) I and II C) II only
A) 0.56 B) 1.12 C) 1.68 D) 2.24 E) 4.48 D) I and III E) I, II and III

Aldehydes and Ketones 105

 DOUBLE PUZZLE
These words have been jumbled up (there are no letters missing). Luckily, clues have been left. Put the correct spelling in the
Answer Grid. Transfer the numbered letters to the reference check, and use this to fill in the SECRET MESSAGE.

ANSWER GRID CONFUSED FORM DEFINITION

O

1
8 NOBRAYCL The C group is known as the _______ group in
organic compounds.

2
14 HEYDEDAL Compounds in which one hydrogen atom and one
carbon atom are bonded to the carbon atom in a
carbonyl group are called ________
3
2 DEFORMHALEYD The simplest member of the aldehydes is __________

4
24 NELSLTOTENGARE It is an ammoniacal solution of silver nitrate, this
mixture is used to distinguish between aldehydes
and ketones
5
13 32 MIPAYRRSCHOOLAL When aldehydes are reduced by one step __________
are obtained

6
6 DECEYHATALDE Two carbon containing aldehyde

7
11 TEKESNO The compounds in which two alkyl groups or aryl
groups are attached to the carbonyl group, are
known as __________
8
20 SOMERIS Aldehyde and ketones that have the same
number of carbon atoms are _______ of each other.

9
10 NKTEEOS Propanone butanone are examples of ________ .

10
23 9 YCESDONARCOLAHSOL Hydrogen is added to ketones using metal catalysts
such as Ni, Pt and Pd to form these compounds

11
5 TONEECA It is the first member of the ketones

12
41 INLAMROF A 40% solution of formaldehyde

13
7 XYBACLICROSICAD These compounds are the oxidation products of
aldehydes

14
12 LIMPES Ketones, which have the same alkyl or aryl groups,
are known as _______ ketones

15
19 RANONEPOP The common name of this compound is ACETONE

REFERENCE CHECK
A B C D E F G H I J K L M N O P Q R S T U V W X Y Z
39 4

SECRET MESSAGE
6 9 17 24 17 41 24 17 6 4 11 6 13 19 17 32 11 2

5 41 24 7 11 8 13 14 5 11 20 19 11 39 8 23 32

41 14 23 17 9 13 23 17 32 41 8 23 10 17 6 11 8 17 32

106 Oxygen And Nitrogen Containing Organic Compounds

 INTRODUCTION
O

carbonyl hydroxyl The group that is formed by the combination of a carbonyl C and hydroxyl
O
C O OH ( OH) group is called the carboxyl C OH group.
Compounds that contain
the carboxyl group are called carboxylic acids.

O Most organic acids found in fruits and vegetables are carboxylic acids.
O
C
OH Carboxylic acids can be represented by R COOH or R C OH .

The R group can be aliphatic, aromatic or cyclic.

carboxyl
1. CLASSIFICATION OF CARBOXYLIC ACIDS
Carboxylic acids can be separated into two groups; according to the number of car-
boxyl groups, or according to the different functional groups in their structures.

1.1. ACCORDING TO THE NUMBER OF CARBOXYL

GROUPS
Depending upon the number of carboxyl groups, acids can be classified as
monocarboxylic acids or polycarboxylic acids.

Monocarboxylic Acids
Acids which contain only one carboxyl group are called monocarboxylic acids.
H COOH CH3 COOH C2H5 COOH
formic acid acetic acid propionic acid

The general formula of monocarboxylic acids is CnH2n+1COOH or CnH2nO2.

Here, n can be any integer.

Polycarboxylic Acids
Acids which contain more than one carboxyl group are called polycarboxylic
acids. If two carboxyl groups are present, the acid is a dicarboxylic acid and if
there are three carboxyl groups the acid is a tricarboxylic acid.

The general formula of a dicarboxylic acid is CnH2n(COOH)2 and general formu-

la of a tricarboxylic acid is CnH2n–1 (COOH)3.
1
COOH
2 COOH
CH2
3 CH2 CH CH2
COOH HOOC CH2 CH2 COOH
1,3–propanedioic acid pentane, 1,3,5–tricarboxylic acid
Malonic acid

108 Oxygen And Nitrogen Containing Organic Compounds

1.2. ACCORDING TO THE FUNCTIONAL GROUPS
Different functional groups may be attached to the carbon chain of a carboxylic
acid. In this case, the classification of the acid is made according to the function-
al group.

Hydroxy Acids
Carboxylic acids which contain the hydroxyl
group are called hydroxy or oxy acids.
CH2 COOH CH3 CH COOH CH2 CH COOH
Hydroxy acids show both alcoholic and acidic
OH OH OH OH
properties because of the hydroxyl ( OH)
oxyacetic acid 2 - oxypropanoic acid 2,3 – dihydroxypropanoic acid
and the ( COOH) carboxyl groups. glycolic acid lactic acid glyceric acid

Amino Acids
Carboxylic acids which contain the amino
group ( NH2) are called amino acids.

Amino acids show basic properties because NH2 NH2 NH2 NH2
of the amino group ( NH2) and acidic
CH2 COOH CH3 CH COOH CH3 (CH2)3 CH COOH
properties because of the carboxyl group
aminoacetic acid 2 – aminopropanoic acid 2,6 – diaminohexanoic acid
( COOH), so they are amphoteric com- glycine a–alanine lysine
pounds. Amino acids act as a base when
they react with an acid and act as an acid
when they react with a base, in both cases a
salt is formed.

Keto Acids
O O O
O
H C COOH CH3 C COOH CH3 C CH2 COOH
The carbonyl ( C ) group in carboxylic 2 – ketoethanoic acid 2 – ketopropanoic acid 3 – ketobutanoic acid
(glyoxalic acid) (pyruvic acid) (acetoacetic acid)
acids leads to keto acids.

2. NOMENCLATURE OF CARBOXYLIC ACIDS

2.1. COMMON NAMES
Carboxylic acids have common names derived from Latin or Greek words that
relate to their natural sources. For example, formic acid is obtained from ant
secretions, in Latin, ant is formica hence the name formic acid. The names of
acetic acid (acetum, vinegar), butyric acid (butyrum, butter) and stearic acid
(stear, tallow) are derived in the same way.

H COOH CH3 COOH C3H7 COOH CH3CH2)16 COOH

formic acid acetic acid butyric acid stearic acid

Carboxylic Acids 109

 If there are different substituents attached to the chain, their positions can be
shown by the Greek letters D–, E–, J–, G–, H– and so on.
g b a g b a
CH3 CH CH2 CH2 COOH CH3 CH CH COOH

OH CI CH3
g – hydroxyvaleric acid a – methyl – b – chlorobutyric acid

Number of Carbon Structure Common Name Source

1 HCOOH Formic acid Ant (L. formica)
2 CH3COOH Acetic acid Vinegar (L. acetum)
3 CH3CH2COOH Propionic acid Milk, butter, and cheese (Greek; protos, first; pion, fat)
4 CH3(CH2)2COOH Butyric acid Butter (L. butyrum)
5 CH3(CH2)3COOH Valeric acid Valerian root (L. valere, being strong)
6 CH3(CH2)4COOH Caproic acid Goats (L. caper)
7 CH3(CH2)5COOH Enanthoic acid Enantic (L. oenanthe, vine blossom)
8 CH3(CH2)6COOH Caprylic acid Goats (L. caper)
9 CH3(CH2)7COOH Pelargonic acid Pelargonium roseum
10 CH3(CH2)8COOH Capric acid Goats (L. caper)

Table 1: Common names of the first ten carboxylic acids and their sources.

2.2. USING THE IUPAC SYSTEM

The longest chain containing the carboxyl group is selected. The chain is num-
bered beginning with the carboxyl carbon atom and substituents are located in the
usual way. The locations of substituents are clarified by the number of the carbon
atom to which they are attached. To obtain the name of the acid, -e from the name
of the corresponding alkane is replaced by the suffix –oic and word acid is added.
3 2 1
H COOH CH3 COOH CH CH COOH
b 3 a
methanoic acid ethanoic acid
CH3
2 – methylpropanoic acid
4 3 2 1 a – methylpropanoic acid
CH2 CH CH2 COOH
g b a
2 1 4 3 2 1
3 – butenoic acid CH2 COOH CH3 CH CH COOH
b – butenoic acid a g b a

3 2 1
2 – phenylethanoic acid 2 – butenoic acid
CH C COOH a – phenylacetic acid a – butyric acid
b a
CI CH3 If a carboxylic acid contains a carboxyl group at each end of the chain, the suf-
2 – methyl – 3 – chloropropenoic acid
fix –dioic acid is added to the name of corresponding alkane.
a – methyl – b – chloropropenoic acid

110 Oxygen And Nitrogen Containing Organic Compounds

 1 1 1
COOH COOH COOH
1 2 2
COOH CH2 CH CH3 (CH2)4
2 3 3 6
COOH COOH COOH COOH
ethanedioic acid 1,3 – propanedioic acid 2 – methyl – 1,3 – 1,6 – hexanedioic acid
oxalic acid malonic acid propanedioic acid adipic acid

If the carboxyl group in a compound is attached to a carbon other than those on

the end of the chain, the prefix carboxy is used together with the location of the
carboxyl group.
If the carboxyl group is attached to a cyclic compound, the words carboxylic acid
are added to the name of cyclic compound.

CH2 COOH
COOH COOH HO C COOH
COOH
CH2 COOH
benzenecarboxylic acid 1,2 – benzenedicarboxylic acid 2 – hydroxypropane –
benzoic acid phthalic acid 1, 2, 3 – tricarboxylic acid
citric acid

1
Give the IUPAC names for the following compounds.
a. CH3CH2CH COOH b. Br CH2 CH COOH

Cl Br

c. CH2 (CH2)4 COOH d. CH2 (CH2)3 COOH

NH2 CN

a. 2 – chlorobutanoic acid b. 2,3 – dibromopropanoic acid

c. 6 – aminohexanoic acid d. 5 – cyanopentanoic acid

2
Write the structural formulae for the following compounds.
a. 2 – methylbutanoic acid
b. 5 – aminopentanoic acid
c. 2 – methyl – 3 – hydroxybutanoic acid
d. 1, 5 – pentanedioic acid
e. D – methyl – E – chloropropanoic acid
f. D – oxypropionic acid

Carboxylic Acids 111

 a. CH3 CH2CH COOH d. CH2 CH2 CH2
CH3 COOH COOH

b. CH2 (CH2)3 COOH e. CH2 CH COOH

NH2 Cl CH3

OH CH3

c. CH3 CH CH COOH f. HO CH COOH

CH3

3. PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS

Butter contains butyric acid. The amount
of butyric acid increases when butter is
spoilt, giving it an unpleasant odor.
The first three members of the saturated monocarboxylic acids are colorless liq-
uids with a sharp odor. Carboxylic acids with carbon numbers between 4 and 9
smell of butter and almond oil. The smell of spoilt butter and cheese and the
unpleasant odor of sweat is due acid formation. For example, butyric acid smells
like butter because it is found in butter.
Carboxylic acids having more than ten carbons are odorless, wax-like solids. The
acids from C14 to C22 are found in vegetable oils and fats and are known as fatty
acids.
Some of the physical and chemical properties of carboxylic acids are dependent
upon the polarity of the carboxyl group. Acid molecules can form strong hydrogen
bonds with each other and as a result carboxylic acid molecules can form dimers.
O H O
R C C R
O H O

The boiling points of carboxylic acids are approximately 30-40 °C higher than
those of hydrocarbons, alcohols, ethers, aldehydes and ketones of comparable
molar mass. For example, ethyl alcohol boils at 78 °C and formic acid at
– 100.5 °C.
d d
+

O O
At room temperature, the C1 to C7 carboxylic acids are liquids and acids with
H
+ more than 7 carbons are solids. Boiling points of carboxylic acids increase with
R C d – C R
d increasing molar mass. However there is no regular change in the melting points
O H O
of carboxylic acids. Carboxylic acids with an even number of carbon atoms melt
at higher temperatures than similar acids with an odd number of carbon atoms.
Because of the strong hydrogen bonds,
carboxylic acid molecules form dimers.

112 Oxygen And Nitrogen Containing Organic Compounds

CH3COOH C2H5COOH C3H7COOH C4H9COOH
m.p. 16.6 °C m.p. –21.5 °C m.p. – 8 °C m.p. –34 °C

Carboxylic acids dissolve in water because they form hydrogen bonds. As the num-
ber of carbon atoms increases, the effect of hydrogen bonding and hence the solu-
bility in water decreases. The alkyl group (R ) has hydrophobic properties so as
the R group becomes larger, the hydrophobic properties of the acids increase.

The first four members of the carboxylic acids are soluble in water in any ratio.
However the solubility of pentanoic acid is only 3.7 grams per 100 grams of
water while that of decanoic acid is 0.2 grams. Higher carboxylic acids can be
dissolved in ether, benzene or chloroform.

Melting Boiling *Solubility

IUPAC Name Common Name Formula
Point (°C) Point (°C) (g/100 mL water)
Methanoic acid Formic acid HCOOH 8.5 100.5 f
Ethanoic acid Acetic acid CH3COOH 16.6 118 f
Propanoic acid Propionic acid CH3CH2COOH – 21.5 141 f
Butanoic acid n – butyric acid CH3(CH2)2COOH –8 164 f
Pentanoic acid n – valeric acid CH3(CH2)3COOH – 19 187 4.97
Hexanoic acid Caproic acid CH3(CH2)4COOH –3 205 1.08
Heptanoic acid Enanthoic acid CH3(CH2)5COOH – 10.5 223 0.26
Propenoic acid Acrylic acid H2C CHCOOH – 13 141 slightly soluble
Benzenecarboxylic acid Benzoic acid C6H5COOH 122 250 0.34

COOH
2 – hydroxybenzoic acid Salicylic acid 159 211 0.22
OH
149 -160
Ethandioic acid Oxalic acid (COOH)2 189 15.00
Sublimes
* at 25°C
Table 2: Physical properties of some carboxylic acids.

When carboxylic acids dissolve in water, hydrogen ions are formed and an equi- –
d + H
librium is established. d
O H O
R COOH(aq) + H2O(l)
R COO–(aq) + H3O+(aq) R C + –
d d
The acid ionization constant is defined by the formula: O H O H
[R COO–] . [H3O+] –
d H
Ka = –––––––––––––––––––––––––––––––
[R COOH]
Carboxylic acids dissolve in water form-
Formic acid has the highest ionization constant (Ka) ing hydrogen bonds with water mole-
– + cules.
HCOOH + H2O
HCOO + H3O
formic acid formate ion

Ka = 1.8 . 10–4

Carboxylic Acids 113

 1.23 A° 1.27A° –
O O
R C + H 2O R C + H3O+
O H O
1.36 A° 1.27A°
resonance hybrid

As the number of carbon atoms increases in an acid, ionization decreases, and

hence the ionization constant (Ka) decreases. Because of the decrease in the
concentration of hydrogen ions, acidic strength decreases as shown in Table 3.

Name Formula Ionization Constant (Ka)

Formic acid HCOOH 1.8 · 10–4
Acetic acid CH3COOH 1.8 · 10–5
Propanoic acid CH3CH2COOH 1.3 · 10–5
2 – methylpropanoic acid (CH3)2CHCOOH 1.6 · 10–5
2,2 – dimethylpropanoic acid (CH3)3CCOOH 0.9 · 10–5
Butanoic acid CH3(CH2)2COOH 1.6 · 10–5
Hexanoic acid CH3(CH2)4COOH 1.30 · 10–5
Fluoroacetic acid FCH2COOH 2.6 · 10–3
Chloroacetic acid ClCH2COOH 1.4 · 10–3
Bromoacetic acid BrCH2COOH 1.3 · 10–3
Dichloroacetic acid Cl2CHCOOH 5.6 · 10–2
Trichloroacetic acid Cl3CCOOH 2.3 · 10–1
Table 3: Ionization constants of some carboxylic acids in water at 25°C.
–
When highly electronegative atoms or polyatoms, such as F, Cl, Br, S, NO2 or
OH– are attached to an acid, acidic strength increases.
The electronegativity of the attached atom or group effects the acidity directly.
For example, as F is more electronegative than Cl, D – fluoroacetic acid is
stronger than D – chloroacetic acid.
Electronegative substances attract electrons from the carbon atoms they are
attached to, this further polarizes the O H bond making ionization of the acid
easier.
–
CH2 COOH + H2O CH2 COO + H3O+ Ka = 2.6 · 10
–3

F F
a – fluoroacetic acid a – fluoroacetate
–
CH2 COOH + H2O CH2 COO + H3O+ Ka = 1.4 · 10
–5

Cl Cl
a – chloroacetic acid a – chloroacetate

114 Oxygen And Nitrogen Containing Organic Compounds

 H CH3 CH3CH2 CH3CH2CH2

As the size of the alkyl group increases, acidic properties decreases

H O H O
H C C H C C + H+
–
Cl O H Cl O
strong electron attraction by chlorine stable anion

Both the location and the number of electronegative substituents effect the acid
strength. If the electronegative substituent is close to the carboxyl group or if the
number of electronegative substituents is high, the polarization of the O H
bond increases and thus acidic strength increases.
g b a g b a g b a
CH2 CH2 CH2 COOH CH3 CH CH2 COOH CH3 CH2 CH COOH

Cl Cl Cl
g – chlorobutanoic acid b – chlorobutanoic acid a – chlorobutanoic acid
K = 3 . 10–5
a K = 8.9 . 10–5
a K = 1.4 . 10–3
a

Cl
a a a
CH2 COOH Cl CH COOH Cl C COOH

Cl Cl Cl
chloroacetic acid dichloroacetic acid trichloroacetic acid
K = 1.4 . 10–3
a K = 5.6 . 10–2
a K = 2.3 . 10–1
a

3
Compare the boiling points of the following compounds.
I. C2H5OH
II. CH3OCH3
III. HCOOH

I, II and III have equal molar masses of 46 g/mol.

I is an alcohol, II is an ether and III is a carboxylic acid.
There is no hydrogen bonding between ethers, so they are volatile. Alcohols and
carboxylic acids both undergo hydrogen bonding, but because of the dimeriza-
tion of carboxylic acids, they have the highest boiling point. Therefore the boil-
ing point order is III > I > II .

Carboxylic Acids 115

 4
Calculate the pH of 0.5 M acetic acid.
(K = 1.8 . 10–5)
a

Acetic acid dissociates into ions in water;

CH3COOH(aq)
CH3COO– (aq) + H+(aq) Ka = 1.8 . 10–5

Initial : 0.5 M – –
Change : –x +x +x
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
at Equilibrium : (0.5–x) M xM xM

[CH3COO–] . [H+] x.x

Ka = ––––––––––––––––––– Ÿ 1.8 . 10–5 = ––––––––– Ÿ x = 3 . 10–3 M
[CH3COOH] (0.5 – x)
+
[H ] = 3 . 10–3 M.
+
pH = – log[H ] = – log (3 . 10–3)
pH = 2.52

4. CHEMICAL PROPERTIES OF CARBOXYLIC ACIDS

The reactions of carboxylic acids can be separated into two groups; bond cleav-
age of the O H bond and bond cleavage of the C O bond. When the O
H bond is broken, H+ is produced and when the C O bond is broken, OH is
produced.

4.1. REACTIONS INVOLVING OF CLEAVAGE OF THE

O — H BOND
From the COOH group, H+ ion leaves and a carboxylate salt forms. To obtain
the name of carboxylate anion, the suffix –oic acid is replaced by the suffix –ate.
For example, CH3COO– is called acetate.

Salt Formation
Carboxylic acids undergo reaction with active metals to form carboxylate salts
and hydrogen gas.
HCOOH + Na o HCOONa + 1/2H2
formic acid sodium formate

2CH3COOH + Mg o (CH3COO)2Mg + H2
acetic acid magnesium acetate

116 Oxygen And Nitrogen Containing Organic Compounds

 5
24 grams of a monocarboxylic acid reacts with an excess amount of Mg and 4.48
L hydrogen gas (H2) is produced at STP. What is the molecular formula of the
carboxylic acid?

Number of moles of H2 gas.

4.48 L
n = ––––––––––––––– = 0.2 mol
22.4 L/mol
Reaction of carboxylic acid with Mg;
2R COOH + Mg o (RCOO)2Mg + H2
amount of carboxylic acid used;
2 mol acid produces 1 mol H2 gas
x mol acid produces 0.2 mol H2 gas
–––––––––––––––––––––––––––––––––––––––––––––––
x = 0.4 mol
molar mass of acid
m m 24 g
n = –––––– o M = ––––– = –––––––––
M n 0.4 mol
M = 60 g/mol.
Molecular formula of the carboxylic acid
CnH2n+1COOH = (n . 12) + [(2n + 1) . 1] + 12 + 16 + 16 + 1 = 60
n=1 and formula is; CH3COOH

Neutralization Reactions
Carboxylic acids react with bases in the same way as inorganic acids do to form
salt and water. Because carboxylic acids are weak acids, their salts hydrolyse in
solution and so carboxylic acid salt solutions show basic properties.
R COOH + NaOH o R COONa + H2O
carboxylic acid inorganic base salt water

HCOOH + NaOH o HCOONa + H2O

formic acid sodium hydroxide sodium formate

2CH3COOH + Ba(OH)2 o (CH3COO)2Ba + 2H2O

acetic acid barium hydroxide barium acetate
COOH COOK
+ 2KOH o + 2H2O
COOH COOK
oxalic acid potassium hydroxide potassium oxalate

Carboxylic Acids 117

 Reactions with Salts
Carboxylic acids react with basic salts, such as CaCO3 and NaHCO3 , to form
CO2, salt and water.

This reaction is used to differentiate between carboxylic acids and phenol and
alcohol compounds, which also contain the OH group. Alcohols and phenols
do not react with these basic salts.

R COOH + NaHCO3 o R COONa + CO2 + H2O

2R COOH + CaCO3 o (R COO)2Ca + CO2 + H2O
C2H5COOH + NaHCO3 o C2H5COONa + CO2 + H2O
2CH3COOH + MgCO3 o Mg(CH3COO)2 + CO2 + H2O

6
Complete the following reactions and give the names of the products.
a. CH3COOH + Zn o b. HCOOH + Al o
COOH
c. C2H5COOH + Ba(OH)2 o d. + KOH o
COOH

e. CH3COOH + KOH o f. CH3COOH + KHCO3 o

g. 2CH3COOH + MgCO3 o

a. 2CH3COOH + Zn o (CH3COO)2Zn + H2
zinc acetate

b. 3CH3COOH + Al o (CH3COO)3 Al + 3/2H2

aluminum acetate

c. 2C2H5COOH + Ba(OH)2 o Ba(C2H5COO)2 + 2H2O

COOH barium
COOK propanoate
d. + 2KOH o + 2H2O
COOH COOK
potassium oxalate
e. CH3COOH + KOH o CH3COOK + H2O
potassium acetate

f. CH3COOH + KHCO3 o CH3COOK + CO2 + H2O

potassium acetate

g. 2CH3COOH + MgCO3 o (CH3COO)2Mg + CO2 + H2O

magnesium acetate

118 Oxygen And Nitrogen Containing Organic Compounds

4.2. REACTIONS THAT INVOLVE C — O BOND BREAKAGE
O O O
The hydroxyl group ( OH) can be separated from the carboxyl group C OH R C R C
by the cleavage of the C O bond.
Cl
O acyl group
acetyl chloride
The R C group is called the acyl group. If a different functional group is derivative of carboxylic acid
attached to the acyl group other than the OH group, the compound is called
an acid derivative.

Formation of Acid Anhydrides

O
If carboxylic acids are treated with dehydrating agents, acid anhydrides are
carboxylate
formed. R C group
O O
O
The functional group of acid anhydrides is the C O C group.
R C acyl group
Acid anhydrides are named by adding anhydride after the acid from which they O
are derived.

O O O O

R C OH + HO C R R C O C R + H OH
carboxylic acid carboxylic acid acid anhydride water
(H+ donor) (OH– donor)

O O O O

CH3 C OH + HO C CH3 CH3 C O C CH3 + H2O

acetic acid acetic acid acetic anhydride

Formation of an anhydride from an acid is similar to the formation of an ether

from alcohols. When dicarboxylic acids are heated up to 200 – 300 °C, cyclic
anhydrides with five or six carbons are formed.

CH2 COOH 200 - 300 °C

O + H2O
CH2 COOH
succinic acid O
succinic anhydride

An alternative way to produce anhydrides is by the reaction of alkali metal salts

of carboxylic acids with acid chlorides. In addition to the anhydride, alkali metal
salts are formed in this reaction.

Carboxylic Acids 119

 O O O O

R C ONa + R¢ C Cl R C O C R¢ + NaCl
sodium salt of acid chloride acid anhydride salt
carboxylic acid

O O

C2H5COONa + C2H5COCl C2H5 C O C C2H5 + NaCl

sodium propionyl propanoic anhydride sodium
propanoate chloride chloride

Esterification
As you may remember from the alcohol chapter, esters are formed by the reac-
tion of a carboxylic acid and an alcohol in the presence of a sulfuric acid, H2SO4,
catalyst.

The hydroxyl group ( OH) of the carboxyl group is replaced by the alkoxide
(R O) group in the esterification reaction.

O O
H2SO4
R C + H O R¢ R C + H O H
alcohol water
O H O R¢
carboxylic acid ester

H2SO4
CH3 COOH + C2H5 OH CH3 COO C2H5 + H2O
acetic acid ethyl alcohol ethyl acetate water

Which carboxylic acid and alcohol pairs should be used to form the esters
below?
O

X : CH3 CH2 C O CH CH3

CH3

Y: C6H5 CH2 O C H

Z : C4H9 COO CH2

C4H9 COO CH2

120 Oxygen And Nitrogen Containing Organic Compounds

 O

In X, the acyl group is CH3 CH2 C , and the alkoxide group is

O CH CH3 . So X is formed from propanoic acid, (C2H5COOH) and
CH3
secondary propanol, CH3CHCH3 .
OH

The acyl group of Y is H C and the alkoxide group is C6H5 CH2 O

Therefore Y is formed from formic acid (HCOOH) and benzyl alcohol

(C6H5CH2OH).
O
Z contains the same two acyl groups C4H9 C and the alkoxide group
CH2 O

CH2 O

The alkoxide group is a derivative of glycol. So Z is formed from pentanoic acid

and glycol (1,2 – ethanediol).

Formation of Acid Chlorides

The hydroxyl group of carboxylic acids is replaced by chloride upon reaction with
PCl3, PCl5 or SOCl2 . To obtain the name of the acid chloride, the suffix –oic acid
is replaced by –oyl chloride.
O O
heat
3R C + PCl3 3R C + H3PO3
phosphorous
OH Cl acid
carboxylic acid acid chloride

heat
RCOOH + PCl5 o RCOCl + POCl3 + HCl
carboxylic acid acid chloride

heat
RCOOH + SOCl2 o RCOCl + SO2 + HCl
carboxylic acid acid chloride

When acid chlorides hydrolyse in water, carboxylic acids form.

O O
R C + H OH R C + H Cl

Cl OH
acid chloride carboxylic acid

Carboxylic Acids 121

 8
Write down the reactions of propanoic acid with the given compounds under
suitable conditions.
a. PCl3 b. PCl5 c. SOCl2

a. 3CH3 CH2 C O + PCl3 3CH3 CH2 C O + H3PO3

OH Cl

b. CH3 CH2 C O + PCl5 CH3 CH2 C O + POCl3 + HCl

OH Cl

c. CH3 CH2 C O + SOCl2 CH3 CH2 C O + SO2 + HCl

OH Cl

4.3. ADDITION OF HALOGENS

When a halogen is replaced by an OH, In the presence of a red phosphorous catalyst, chlorine and bromine react with
NH2, SH or CN group, a carboxylic acids to produce D – halo acids. When excess amounts of halogen are
hydroxy acid, amino acid, thiohydroxy used, the number of substituted hydrogens increases.
acid or cyano acid is produced.
H H X
P P
R C COOH + X X R C COOH + X X R C COOH
– HX – HX
H X X
a – halocarboxylic a, a – dihalo
acid carboxylic acid

Cl Cl
+Cl2 / P +Cl2 / P +Cl2 / P
CH3COOH – HCl CH2 COOH – HCl CH COOH – HCl Cl C COOH
acetic acid
Cl Cl Cl
chloroacetic acid dichloroacetic trichloroacetic
acid acid

4.4. REDUCTION REACTIONS

The reduction of carboxylic acids is difficult by catalytic hydrogenation.
Carboxylic acids have to be reduced by strong reducing agents such as LiAlH4
or NaBH4. The COOH group is reduced directly to CH2OH.
LiAlH4
R COOH o R CH2 OH

122 Oxygen And Nitrogen Containing Organic Compounds

5. PREPARATION OF CARBOXYLIC ACIDS
5.1. OXIDATION OF PRIMARY ALCOHOLS AND ALDEHY-
DES
Oxidation of primary alcohols produces aldehydes, and oxidation of aldehydes
produces carboxylic acids. For these oxidation reactions KMnO4 and K2Cr2O7
solutions are used in acidic medium.

O O
[O] [O]
R CH2 OH – H2O
R C R C
primary alcohol
H OH
aldehyde carboxylic acid

H3C H3C O H3C O

[O] [O]
CH CH2 OH CH C CH C
– H2O
H3C H3C H H3C OH
isobutanol isobutanal isobutanoic acid

If an excess amount of oxidizing agent is used, primary alcohols are oxidized to

carboxylic acids directly.

O O
[O] [O]
CH2OH C C
– H 2O
H OH
benzyl alcohol benzaldehyde benzoic acid

5.2. OXIDATION OF AROMATIC COMPOUNDS

Benzoic acid is prepared by the oxidation of alkyl benzenes. For the oxidizing
agent, a hot, acidic solution of KMnO4 or K2Cr2O7 is used. The number of
carbon atoms attached to the aromatic structure, doesn't change the prod-
uct.

KMnO4 or K2Cr2O7
CH3 heat COOH + H2O

methyl benzene benzoic acid

(toluene)
KMnO4 or K2Cr2O7
CH2 CH3 heat
COOH + 2H2O + CO2

ethyl benzene benzoic acid

Carboxylic Acids 123

 5.3. OXIDATION OF ALKENES
When alkenes react with a hot, basic solution of KMnO4 they are oxidized to car-
boxylic acids. If straight chain alkenes are used, monocarboxylic acids are pro-
duced.

KMnO4, OH–
R CH CH Rc o R COOH + Rc COOH
heat

KMnO4, OH–
CH3 CH CH C2H5 o CH3 COOH + C2H5 COOH
heat

If cycloalkenes are used, dicarboxylic acids are produced.

KMnO4
CH2 CH2 CH2 CH2

COOH COOH
cyclohexene
1,6 – hexandioic acid

5.4. CARBONATION OF GRIGNARD REAGENTS

Preparation of carboxylic acids by the reaction of Grignard reagents with carbon
dioxide is the most commonly used method.
R MgX + O C O R C O
Grignard
compound OMgX

R C O + HX R C O + MgX2

OMgX OH
carboxylic acid

Carbonation of Grignard reagents is similar to the addition of Grignard reagents

to aldehydes and ketones. However, in the former reaction, carboxylate is pro-
duced, not alcohol. The magnesium carboxylate produced does not dissolve in
ethers but when dissolved in acid, carboxylic acids are formed.

O O
+HBr
CH3 MgBr + CO2 CH3 C O MgBr CH3 C OH
–MgBr2
methyl magnesium acetic acid
bromide

5.5. HYDROLYSIS OF CARBOXYLIC ACID DERIVATIVES

H2O or the OH– ion may react with the carbonyl group of an ester to form car-
boxylic acids. For example esters can be hydrolyzed by heating with water in the
presence of an acid catalyst.

124 Oxygen And Nitrogen Containing Organic Compounds

 O O
+
H
R C OR¢ + H OH R C OH + R¢ OH
ester carboxylic acid alcohol

O O
+
H
CH3 C OCH3 + H OH CH3 C OH + CH3 OH
methyl acetate acetic acid methyl alcohol

5.6. HYDROLYSIS OF NITRILES

Carboxylic acids are produced by the hydrolysis of nitrile compounds. In the
hydrolysis the CN group is converted to the COOH group. Nitriles can be
prepared by substitution reactions of alkyl halides with KCN or NaCN.
+
+2H O,H
2
CH3 CH2 Cl + NaCN CH3 CH2 CN +
CH3 CH2 COOH
– NaCl –NH
4
propiononitrile propanoic acid
+
4H2O,2H
CH2 CH2 CH2 + 2NaCN CH2 CH2 CH2 +
CH2 CH2 CH2
– 2NaBr –2NH4
Br Br CN CN COOH COOH
1,3 dibromopropane pentanodinitrile 1,5 pentanedioic acid
glutaric acid

5.7. REACTION OF CARBOXYLATE SALTS

When carboxylate salts react with acid halogens or their solutions, carboxylic
acids are formed.
R COONa + HX R COOH + NaX (X = Cl, Br, I)
carboxylate salt carboxylic acid

CH3 COONa + HCl CH3 COOH + NaCl

sodium acetate acetic acid

9
Write equations for the transformations below indicating conditions and cata-
lysts.
a. n – pentanoic acid from n – pentanol
b. 1,5 – pentanedioic acid from cyclopentene
c. Benzoic acid from chlorobenzene
d. 1,4 – hexandioic acid from 1,4 – dibromobutane
e. Formic acid from ethyl formate

Carboxylic Acids 125

 O O
[O] [O]
a. C4H9 CH2 OH C4H9 C C4H9 C
– H2O
H OH
n – pentanol n – pentanoic acid

KMnO4
b. CH2 CH2 CH2

COOH COOH
cyclopentene 1,5 – pentanedioic acid

Cl NaCN CN +2H2O, H+ COOH

c. + NH +
– NaCl 4

chlorobenzene benzoic acid

+2NaCN +4H2O, H+ +
d. CH2 (CH2)2 CH2 –2NaBr
CH2 (CH2)2 CH2 CH2 (CH2)2 CH2 + NH4

Br Br CN CN COOH COOH
1,4 – dibromobutane 1,6 – hexanedioic acid

O O
H+
e. H C OC2H5 + H2O H C OH + C2H5OH
ethyl formate formic acid

6. SOME COMMON CARBOXYLIC ACIDS

6.1. FORMIC ACID
Formic acid is the simplest carboxylic acid (HCOOH).
In nature, it is found in the stings and bites of many insects, including bees and
ants. The name “formic” is derived from the Latin name for ant, formica.

Physical Properties
Formic acid is miscible with water and slightly soluble in hydrocarbons. It disso-
ciates into ions in aqueous solution:
HCOOH(aq)
HCOO–(aq) + H+(aq) Ka = 1.8 · 10–4
Ants have formic acid.
It is a colorless, pungent, fuming and corrosive liquid with a boiling point of
100.5°C.

The strongest monocarboxylic acid is
formic acid.
Chemical Properties
If the structure of formic acid is examined, it is seen to contain both an aldehyde
and a carboxyl group. For this reason, unlike other organic acids, formic acid and
its salts can be oxidized. When it is oxidized, it first produces carbonic acid (an
unstable intermediate) and then carbon dioxide and water.

126 Oxygen And Nitrogen Containing Organic Compounds

 O O O

H C OH H C OH H C OH

aldehyde carboxyl hydrogen containing hydroxyl containing

group group carboxyl group aldehyde group

O O
[O]
H C OH HO C OH H2O + CO2
formic acid carbonic acid
unstable intermediate The stings of bees contain formic acid.
A bee sting should be treated with dilute
As formic acid contains the aldehyde group it reacts with Fehling’s and Tollens’ ammonia solution.
reagents.

H COOH + 2Ag+ + 2OH– 2Ag + CO2 + 2H2O

When formic acid is heated it decomposes into CO and H2O, though if H2SO4
is used as a catalyst, the reaction occurs at a lower temperature.

heat
HCOOH o CO + H2O

10
How many grams of pure formic acid must be used to precipitate 6.48 grams of
silver upon reaction with an excess amount of Tollens’ reagent?
(HCOOH : 46 g/mol, Ag : 108 g/mol)

Formic acid reaction with Tollens’ reagent;

HCOOH + 2Ag+ + 2OH– o 2Ag + CO2 + 2H2O

46 g formic acid (2 . 108) g Ag

x g formic acid 6.48 g Ag
—————————————————————————
x = 1.38 g formic acid is used

Production
The most widely used methods to produce formic acid are from the oxidations
of methanol and formaldehyde.
Bees secrete formic acid.

Carboxylic Acids 127

 1. In industry, the sodium salt of formic acid is produced from the reaction of
CO and NaOH under high pressure and temperature. This salt is then react-
ed with H2SO4 and H3PO4, to produce formic acid.

200 °C, 10atm

CO + NaOH o HCOONa
sodium formate

200 °C, 10atm

HCOONa + H2SO4 o H COOH + NaHSO4
sodium formate formic acid

2. In the laboratory formic acid can be produced by heating an aqueous solu-

tion of oxalic acid in the presence of glycerine.

COOH
heat
HCOOH + CO2
COOH formic acid
oxalic acid

Uses
Formic acid, like formaldehyde, has good disinfectant properties. It exists
oxalic acid,
water and in honey preventing it from being spoilt easily. It is also used in textile dying
glycerine cold water
and leather tanning. In addition, formic acid is a starting material in the
production of fertilizers, rubbers and plastics. Plus the calcium salt of
formic acid
formic acid is a good softener when dissolved in water.
Production of formic acid in the laboratory

6.2. ACETIC ACID

Acetic acid an important carboxylic acid. It is found in vinegar at a concentration
of around 4-6%. It has the characteristic odor and taste of vinegar and in fact,
the name acetic acid is derived from “acetum” meaning vinegar in Latin. Pure
acetic acid solidifies at 16.7 °C and takes on an ice-like appearance. For this rea-
son solid acetic acid is also known as glacial ethanoic acid.

Physical Properties
Pure acetic acid is a colorless, crystalline compound that melts at 16.7°C and its
boils at 118°C.

It is miscible with water but its ionization percentage is very low, about 3%.

CH3COOH(aq)
CH3COO–(aq) + H+(aq) Ka = 1.8 . 10–5

Chemical Properties
Acetic acid shows all the characteristic properties of carboxylic acids. Hydrogen
gas and acetate salts are formed upon reaction with metals and it undergoes
neutralization reactions with bases and basic salts.

128 Oxygen And Nitrogen Containing Organic Compounds

Production
1. Acetic acid can be produced by the enzyme-catalyzed oxidation of ethyl alco-
hol. The brown acetic acid in vinegar is produced from fruit juices (apple or
grape juice) and is known as natural acetic acid.
2[O]
CH3 CH2 OH CH3 C O + H2O
ethyl alcohol
OH
acetic acid

2. Acetic acid, unlike formic acid, cannot be oxidized easily. Thus, acetates can
be reacted with H2SO4 to produce acetic acid. As mentioned earlier, acetate
produced by the condensation of wood can be precipitated as calcium
acetate using limewater. Methanol and acetone are evaporated from the mix- Acetic acid reacts with egg shells to
ture and if the remaining calcium acetate is reacted with H2SO4, 99.5% pure produce CO2.

acetic acid is obtained.

calcium
3. In industry, the aldehyde formed by addition of water to acetylene is oxidized acetate

to produce acetic acid.

acetic acid
O O
HgSO4 [O] water
H C C H + H2O CH3 C H CH3 C OH
H2SO4
acetylene acetaldehyde acetic acid

Production of acetic acid from calcium

acetate
11
How many liters of H2 gas at STP would evolve from the reaction
of 150 grams of 18% acetic acid solution with excess magne-
sium?
(CH3COOH : 60 g/mol, Mg: 24 g/mol)

Mass of pure acetic acid Ÿ m = 150 g (18/100) = 27 g

Mole number;
m 27 g
n = –––––– = ––––––––––– = 0.45 mol
M 60 g/mol
The reaction equation of acetic acid with Mg;

2CH3COOH + Mg o (CH3COO)2 Mg + H2 n
0.45 mol 0.225 mol

VH = 0.225 mol · 22.4 L/mol = 5.04 L

2

Carboxylic Acids 129

 Uses
Acetic acid is used as a solvent for resins and oil. Its salts are as important as the
acid itself. For example, methane is produced from sodium acetate and acetone
is produced from calcium acetate. Aluminium acetate is used in dyeing as a mor-
dant, for proofing paper and fabrics and in pharmacy as an antiseptic and astrin-
gent. Cellulose acetate, an acetic acid derivative, is used in lacquers, shatter- proof
glass, varnishes and as a fiber. Acetic acid is also the starting material in the pro-
duction of rubber.

UNSATURATED CARBOXYLIC ACIDS AND THEIR POLYMERS

Carboxylic acids that contain a double bond in their structure are called unsaturated carboxylic acids. Examples of these acids
are propenoic acid, 2–methylpropenoic acid, trans-2-butenoic acid, cis-2-butenoic acid.

H3C H H H
CH3 C C C C
CH2 CH COOH CH2 C COOH H COOH H3C COOH
propenoic acid 2–methylpropenoic acid trans–2–butenoic acid cis–2–butenoic acid
acrylic acid meta acrylic acid isocrytonic acid

ACRYLIC ACID (Propenoic acid, vinyl formic acid)

Acrylic acid and its fumes have a pungent, unpleasant odor and are a strong irritant. It is miscible with water, alcohol, chloro-
form and ether. It polymerizes easily in the presence of oxygen and has a boiling point of 141°C. Acrylic acid is obtained from
the oxidation of allyl alcohol or acrylaldehyde.
O
2[O]
CH2 CH CH2OH CH2 CH C
–H2O
OH
allyl alcohol acrylic acid

O O
[O]
CH2 CH C CH2 CH C
H OH
acrylaldehyde acrylic acid

Orlon is used for producing

When it is heated, a glacial resin is produced. carpets and clothing.

n CH2 CH COOH CH2 CH

acrylic acid
COOH
n
polyacrylic acid

130 Oxygen And Nitrogen Containing Organic Compounds

Acrylonitrile polymerizes to form polyacrylonitrile or orlon (acrilan).

n CH2 CH CH2 CH
CN CN
acrylonitrile n
polyacrylonitrile
Orlon

Acrylonitrile is produced by the addition of HCN to acetylene

HC CH + H CN H2C CH CN
acetylene hydrogen acrylonitrile
cyanide
Acrylic paints contain a co-polymer
META ACRYLIC ACID of methyl methaacrylate, They are
rather expensive but highly resist-
Its IUPAC name is 2-methylpropenoic acid and it is well known from its reaction with
ant to water.
methyl alcohol to produce the ester, methyl methacrylate.

CH3 CH3
CH2 C COOH + CH3 OH CH2 C C O + H2O
meta acrylic acid methyl alcohol
O CH3
methyl methaacrylate

Methyl methacrylate forms a polymer, a colorless liquid insoluble in water and glass-like, that is used in manufacturing contact
lenses and shatterproof glass.

CH3 CH3

n CH2 C COOCH3 CH2 C

methyl methaacrylate
COOCH3
n
plexiglas

Polymers of methyl
methaacrylate are used
in manufacturing highly
transparent and resistant
contact lenses.

Polymers of methyl methaacrylate

are also used in the manufacture of
shatterproof security glass.

Carboxylic Acids 131

 7. DICARBOXYILIC ACIDS
These are compounds with two carboxyl (–COOH) groups in their structure.
Their general formula is HOOC – (CH2)n – COOH. All dicarboxylic acids have
common names.

COOH COOH COOH

COOH CH2 (CH2)2 (CH2)4

Tomatoes are vegetables that contain COOH COOH COOH COOH

oxalic acid and its salts. oxalic acid malonic acid succinic acid adipic acid
ethanedioic acid propanedioic acid butanedioic acid hexanedioic acid

Some dicarboxylic acids are important monomers used in synthesizing polymers.

For example, adipic acid (COOH(CH2)4COOH) is used for synthesizing nylon.

In dicarboxylic acids, ionization of the second carboxyl group occurs less readily
than the ionization of the first. Thus, Ka1 values of dicarboxylic acids are bigger
than their Ka2 values.

7.1. OXALIC ACID

This occurs as a free acid in beet leaves, sorrel, spinach, asparagus, tobacco,
and tomatoes. Its name comes from Latin “oxolis” which means “sorrel” one of
the acid's primary sources.

Oxalic acid occurs in the leaf blades of
rhubarb. Pure oxalic acid is a white crys-
talline solid.
Physical Properties
Oxalic acid is a white, crystalline solid. Its melting point is 189 °C though it sub-
limes at 157 °C. It is poisonous, the calcium salt of oxalic acid precipitates in the
kidneys.
Oxalic acid is the strongest of the dicarboxylic acids.

Chemical Properties
When it is heated with glycerine, oxalic acid decomposes into formic acid and
carbon dioxide.

COOH glycerine
HCOOH + CO2
heat
COOH

Oxalic acid is a reducing agent, and can be easily oxidized by acidified KMnO4.
+3 +7 +4 +2
5(COOH)2 + 2KMnO4 + 3H2SO4 10CO2 + K2SO4 + 2MnSO4 + 8H2O

132 Oxygen And Nitrogen Containing Organic Compounds

Production
1. Oxalic acid is made from its sodium salt, and this in turn is obtained from
heating sodium formate.

heat
COO Na
2HCOONa + H2
sodium formate COO Na
sodium oxalate

COO Na COOH
+ H2SO4 + Na2SO4 Oxalic acid salts can be obtained from
COO Na COOH some plants, such as asparagus.
sodium oxalate oxalic acid sodium sulfate

Oxalic acid salts can be obtained directly from some plants. They can also be
obtained by passing CO2 through Na or K at 300-350°C and high pressure.

heat
COONa
2CO2 + 2Na
pressure
COONa
sodium oxalate

2. Oxidation of glycol results in oxalic acid. This process must be carried under
controlled conditions as the reaction may continue and form carbon dioxide.

CH2OH [O] HC O [O]

COOH [O] COOH [O] COOH
– H2 O – H2O
CH2OH CH2OH CH2OH HC O COOH
glycol glycol aldehyde glycolic acid glyoxalic acid oxalic acid

Uses
Because of its reducing properties, oxalic acid is used to bleach wood cellulose,
hay and feathers. It is also used in the manufacture of ink.

7.2. MALONIC ACID

This was first obtained from the oxidation of malic acid (apple acid) and takes its
COOH
name from this. It occurs in the mixed calcium salts obtained during the process-
heat
ing of sugar beet. CH2 CH3 COOH + CO2
acetic acid
It is a colourless liquid that boils at 136 °C. It dissolves in both water and alcohol COOH
malonic acid
and decomposes into acetic acid above 140 °C.

Malonic acid undergoes all the characteristic reactions of dicarboxylic COOH

+2H2O
acids. Its esters are used in organic synthesis. CH2 COOH H2C + NH3

Malonic acid can be obtained from the hydrolysis of cyanoacetic acid. CN COOH
cyanoacetic acid malonic acid

Carboxylic Acids 133

 7.3. ADIPIC ACID
Its name comes from “adeps”, meaning “oil” in Latin, due to the fact adipic acid
was first obtained from oils.

When it is heated it forms cyclopentanone.

300 °C
CH2 (CH2)2 CH2 O + CO2 + H2O

COOH COOH
adipic acid cyclopentanone
Manufacture of nylon.

Adipic acid is a solid with a melting point of 153 °C. It is produced from the oxi-
dation of cyclohexanol with a nitric acid catalyst.

H
%65 HNO3 %65 HNO3
O CH2 (CH2)2 CH2
30–40 °C 30–40 °C
OH
COOH COOH
cyclohexanol cyclohexanone
adipic acid
(1,6 – hexanedioic acid)

If forms long chain polymers upon reaction with diamines and is largely used in
the manufacture of nylon.

H H

n CH2 (CH2)2 CH2 + nN (CH2)6 N –H2O

HOOC COOH H H
adipic acid hexamethylene diamine

H H

Hexamethylene diamine is dissolved in OC (CH2)4 CO N (CH2)6 N

water (bottom layer) and adipic chloride is
n
dissolved in hexane (upper layer). Nylon Nylon 66
is formed between these two layers

8. FATTY ACIDS
Fatty acids are long chained carboxylic acids. Most of the carboxylic acids in the
fatty acids fraction are found as esters of glycerol. The simplest member of the
fatty acids is butyric acid, this has four carbon atoms. (C3H7COOH).

Fatty acids can be classified as saturated or unsaturated.

134 Oxygen And Nitrogen Containing Organic Compounds

8.1. SATURATED FATTY ACIDS

Palmitic Acid (C15H31COOH)

This is a white crystalline solid with a melting point
of 63 °C. It occurs in palm oil, beeswax and other
animal and vegetable fats and oils. It is insoluble in
water but soluble in alcohol and ether.

Stearic Acid (C17H35COOH)

This is a crystalline solid with a melting point of
70 °C. It is soluble in ether and hot alcohol. Stearic
acid is one of the most common fatty acids and
Candles are a mixture of The simplest member of the fatty acids
occurs in the form of glycerides in most animal and stearic acid and palmitic is butyric acid.
vegetable fats. A solid mixture of stearic and acid.
palmitic acid is used to make candles.

8.2. UNSATURATED FATTY ACIDS

Fatty acids which contain a carbon-carbon double bond on the chain attached
to the carboxyl group are called unsaturated fatty acids.

Oleic Acid (C17H33COOH)

This generally occurs in the form of glycerides in olive, almond, cotton and sun-
flower oils. Oleic acid is a colorless, tasteless and odorless liquid with a melting Coconuts contain palmitic acid.
point of 13 °C. It forms one third of the total fatty acids in cow’s milk and is used
in the production of lubricants, detergents, resins and other products. Stearic
acid is formed by the addition of hydrogen to oleic acid.

Linoleic Acid (C17H31COOH) and Linolenic

Acid (C17H29COOH)
These two acids occur widely in the form of glycerides in vegetable oils such as
linseed, sesame and poppy oils. Linoleic acid has two double bonds within the
alkyl chain, where linolenic acid has three.

CH3(CH2)4 CH = CHCH2CH = CH (CH2)7 COOH

linoleic acid Almond oil contains oleic acid.

CH3CH2CH = CH CH2CH = CH CH2CH = CH (CH2)7COOH

linolenic acid

In saturated fatty acids, the alkyl chains are aligned in a zig-zag shape due to the
tetrahedral geometry surrounding the carbon atoms. This structure spreads out
the molecules, keeping van der Waals forces at a maximum.

Carboxylic Acids 135

 To test if a fat contains unsaturated fatty acids it is dipped into an erlenmayer flask
filled with bromine gas. If the bromine color disappears, the fat contains unsatu-
rated fatty acids.

In unsaturated fatty acids, the (C=C) atoms enter this zig-zag shape with a 120°C
geometry, causing the molecules to form a spiral structure.
Naturally occuring fatty acids have a cis geometry. This cis-structure decreases
the melting points of the acids and hence increasing the number of double bonds
in unsaturated fatty acids decreases the melting point.

9. OXYACIDS
Organic acids with a hydroxy group(–OH) in addition to the carboxyl group are
called oxyacids or hydroxy acids. The –OH functional group in oxyacids gives the
compound alcohol properties.

Most oxyacids occur in plants and fruits. They may also contain more than one
hydroxy group (–OH).
COOH COOH

COOH CH OH CH OH CH COOH

CH2 OH CH3 CH2 OH OH

glycolic acid lactic acid glyceric acid mandelic acid
milk acid almond acid

COOH COOH

CH OH CH OH CH2 COOH

CH2 CH OH HO C COOH

COOH COOH CH2 COOH

malic acid tartaric acid citric acid
apple acid grape acid lemon acid
Fruits contain oxyacids.

136 Oxygen And Nitrogen Containing Organic Compounds

Oxyacids form strong hydrogen bonds with water since they have both hydroxy CH2 COOH
(–OH) and carboxyl (–CO2H) groups. Thus, they are highly soluble in water.
HO C COOH
Production CH2 COOH
D–hydroxy acids can be obtained by the hydrolysis of nitriles starting from the rel-
evant aldehyde or ketone.
O OH OH
HCN 2H2O, H +
R C R R C CN R C COOH + NH4+
heat
aldehyde
R R
or ketone
a – hydroxy acid

OH OH
HCN 2H2O, H+ Citric acid (lemon acid)
CH3 C O CH3 C CN heat CH3 C COOH + NH4+

H H H
ethanal a – hydroxypropionic acid

OH OH
2H2O, H +
HCN
CH3 C O CH3 C CN heat
CH3 C COOH + NH4+

C2H5 C2H5 C2H5

2 – butanone a – methyl – a – hydroxy COOH
butanoic acid
CH OH
Carbonic Acid CH OH
Carbonic acid is the simplest member of the hydroxy acids. It is classified as an
COOH
inorganic acid because of its carbonate and bicarbonate salts. However, it may
Tartaric acid (grape acid)
also be considered an organic acid as it contains both the hydroxy and carboxyl
groups.

HO C OH

In carbonic acid there is a hydroxy COOH

group attached to a carboxyl group
CH OH
Carbonic acid can not be isolated and is formed only in aqueous solution by dis-
CH2
solving CO2 gas in H2O. It is a very unstable compound and is easily ionized to
–
H+ and HCO3 ions in water. COOH
+
CO2(g) + H2O(l)
H2CO3(aq)
H (aq) + HCO 2–(aq)
3

All kind of fizzy drinks (cola, mineral water, etc.) contain carbonic acid. Under
lowered pressures carbonic acid decomposes to CO2 and H2O. Malic acid (apple acid)

Carboxylic Acids 137

 10. OPTICAL ISOMERISM
From common experience we know that a right hand glove doesn’t fit on a left
hand and vice-versa. This is because our right and left hands are not identical
but mirror-images of each other; they are non-superimposable. Molecules that
have nonsuperimposable mirror images are called chiral. In our daily life we
encounter many different examples of chirality; our feet, spiral shells and screws.
Most bio molecules in plants and animals are chiral molecules. They exist in
nature as a single type of chiral molecule (either the left or right hand image).

The mirror image of a left hand is a right
hand.
For example, 20 naturally occuring amino acids exist in nature and all of these
molecules are the left hand type. Natural sugar molecules exist as the right hand
type.
A chiral molecule and its non-superimposable image are called enantiomers. So
isomers that are mirror images of each other are enantiomers. For molecules to
have enantiomers, their structure must be asymmetrical. The simplest asymmet-
rical molecule is the tetrahedrally bonded carbon atom with four different types
of atoms or groups attached to it. These kinds of carbon atoms are called asym-
metric or chiral carbon atoms and the molecules are called chiral molecules.
Some compounds may occur in nature with both enantiomers present. For
example, lactic acid can be found in nature this way.

c.

a. b.

isomer II
OH
COOH isomer II

CH3
isomer I

isomer I
isomer I

Enantiomers of lactic acid:

isomer II
a. –OH, –CH3 and –COOH groups are arranged within the molecule in a
clockwise direction.
b. I and II isomers are mirror images of each other.
c. The two isomers are not superimposable.

138 Oxygen And Nitrogen Containing Organic Compounds

Let us examine lactic acid to understand how molecules can exist as two enan-
tiomers.

The central carbon atom of lactic acid has four different atoms or groups
attached to it; –H, –OH, –CH3 and –COOH. Interchanging any two groups on
the central atom converts one enantiomer to the other.

When we put isomer I in front of a mirror the image seen in the mirror is the
image of isomer II. However, the image and isomer I are not superimposable.
Therefore, the two nonsuperimposable molecules are enantiomers of each other.

Enantiomers can be represented by the letters D and L according to their geom-

etry. If the rotation of the plane (see below) is to the right the substance is dex-
trorotatory (Latin: dexter, means right); if the rotation is to the left, the substance
is laevorotatory (Latin: laevus, means left). For example, the enantiomer of lactic
acid formed in sour milk is D-lactic acid, the other, which is found in muscles and
produced in high amounts after performing heavy exercise, causing cramps, is
L-lactic acid.

Enantiomers of a chiral molecule have identical melting and boiling points, den-
sities, and other physical and chemical properties. However, enantiomers show
different behaviour towards plane-polarized light. When a beam of plane polar-
ized light passes through an enantiomer, the plane of polarization rotates. For
this reason chiral molecules are known as optical isomers and are said to be opti-
cally active.

0°

“Polarized light consists of electromag-

+90°
netic waves vibrating along one direc-
–90°
tion”
180°

Enantiomers show different characteristics in terms of their biological properties.

The molecules involved in the metabolisms of animals and plants are mostly chi-
ral molecules and the reactions of different enantiomers occur at different rates.
We may think of the glove and hand analogy; although we are able to put a left-
handed glove onto a right hand, this process takes a lot of time and the glove
doesn’t fit correctly.

Carboxylic Acids 139

 Naturally occuring amino acids are D-isomers and the enzymes that react with
these amino acids are also D-isomers. Consequently, enzyme structures are
essential in controlling the rates of reactions of enantiomers.
The synthesis of chiral molecules in laboratories results in the formation of a
racemic mixture, an equal percentage mixture of both enantiomers. The extrac-
tion of enantiomers from racemic mixtures is almost impossible because of the
identical physical and chemical properties of the enantiomers. Racemic mixtures
are optically inactive, as they contain equal amounts of the D and L isomers.
Some big organic molecules may contain more than one asymmetric carbon
atom in their structure. An increasing number of asymmetric carbon atoms (n)
increases the number of enantiomers by a factor of 2n.
For example glucose contains 4 different asymmetric carbon atoms. Thus, glu-
cose has 16 optical isomers (24), of which 8 are D, and 8 are L enantiomers.

I. Enantiomer II. Enantiomer

C C

A chiral molecule and its non-superimposable image are called enantiomers.

140 Oxygen And Nitrogen Containing Organic Compounds

 12
How many asymmetric carbon atoms do the molecules below contain?

a. CH2 OH b. COOH c. COOH

CH OH CH OH C CH3

COOH COOH CH

CH3

d. CH OH e. CH3 f. CH2 OH

CH2 H C OH CH OH
CH2 C O
CH3 H

H OH OH

a. H C OH b. C O c. C O

H C* OH H C OH C CH3

C O C O C H

OH OH H C H

H H

d. H C OH e. H C H f. H C OH
*
H C H H C* OH H C OH

H C H C O

H C H H

a, e and f have one asymmetric carbon atom (shown by *, sign) each, and the
others don’t have any.
An asymmetric carbon is determined by examining each group bonded to the
atom. The carbon atom must have four bonds and all the groups or atoms
attached to it must be different.

Carboxylic Acids 141

1. What is the general structure of a carboxylic acid? What 7. Write the names and formulae of all isomers of the car-
are the differences between carboxyl compounds and boxylic acid with the general formula C5H10O2.
aldehydes and ketones?

2. Is there any difference between the term “carboxylic 8. Name the following compounds using both the IUPAC
acid” and “organic acid”? Explain. system and their common names.
Cl
O
3. Which of the following compounds are carboxylic acids? a. C OH

O O
CH3
a. CH3 C OH d. H C CH2 OH
Br
O O O

b. HO C CH2 CH3 e. H C CH2 CH3 b. C OH

HO CH3
c. O f. C O
O CH3 CH3
OH
c. HO C CH2 CH CH

Cl

4. Give the approximate values of angles d. Cl CH COOH

O
a, b, c and d between the bonds in a b
d H CN
acetic acid? C
H3C c O

5. A monocarboxylic acid contains 55.8% C, 7% H and

9. Name the following carboxylic acids using the IUPAC
37.2% O by mass. What is the molecular formula of this
compound? (C: 12 g/mol, O: 16 g/mol, H: 1 g/mol) system.

H3C H
a. C C
6. Classify the following carboxylic acids according to both H CH2 COOH
the number of their carboxyl groups and their functional
O O
groups.
b. HO C CH CH2 CH2 C OH
CH2 COOH
CH3
a. CH2 CH2 COOH c. HO C COOH
NH2 CH2 COOH c. CH3 CH CH2 COOH

CH3
O

b. CH2 CH COOH d. HO CH2 C CH2 COOH d. CH3 CH CH CH COOH

COOH OH CN

142 Oxygen And Nitrogen Containing Organic Compounds

10. Write out the molecular formulae of the carboxylic acids 15. Show the hydrogen bonds formed between two acetic
below. acid molecules
a. 2-oxypropanoic acid
b. 2,3-dimethylbutanoic acid
c. 3-amino-4-bromopentanoic acid
d. 3-hydroxy-4-methylhexanoic acid 16. I. CH3CH CHCH3
e. cis-2-butenoic acid II. HCOOH
f. o-methylbenzoic acid III. CH3CH2CH3
g. D-chlorovaleric acid
Compare the above molecules according to their solu-
h. cis-2-valeric acid
bility in water.
i. E-hydroxybutyric acid
j. 2-methyl-1,4-butanedioic acid

17. Compare the solubility of C17H35COOH and

11. Give the common names of the following acids.
C17H35COONa in;
a. Ethanoic acid
b. Ethandioic acid a. Water
c. Butanoic acid b. Ether
d. Pentanoic acid

12. Give the IUPAC names of following acids. 18. Explain the reasons for the large differences between the
boiling points of the given compounds despite their sim-
a. Oxalic acid
ilar molecular masses?
b. E-oxyvaleric acid
Compound Molar Mass Boiling Point
c. Adipic acid (g/mol) (°C)
d. Malonic acid ——————— ————————— ———————
ethyl alcohol 46 78
diethyl ether 46 –25
13. Explain why carboxylic acids dissolve in water better than propane 44 –42
alcohols.
formic acid 46 100.5

14. Which of the following represents a hydrogen bond

formed by the dissociation of a carboxylic acid in water?
Explain. 19. Write out the ionization reaction of acetic acid in water
and show the conjugate acid-base pairs.
I. O H II. O
C H O C H
R O H R O
H H
20. Does hexanoic acid or sodium hexanoate dissolve better
O
in water? Explain.
III. O
H H
O
C H
21. Which has the highest boiling point, acetic acid or
R O
potassium acetate? Explain.

Carboxylic Acids 143

22. Acetic acid, also known as vinegar acid, has a specific 29. Classify the following compounds according to their
odor. A 3% by mass solution of sodium acetate solution functional groups.
has almost the same odor as acetic acid. Explain.
O O O

a. C6H5 C O C C6H5 b. CH3 CH2 C Cl

23. The hydrogen ion concentration of a 400 mL solution c. CH3 CH2 CH CN d. C6H5 CH2 COOH
containing 0.2 mole of a monocarboxylic acid is OH
3 . 10–3 M. Using this information,
a. Find ionization percentage of this acid.
b. What is the Ka value of this acid?

30. If 0.1 mole of HCl is added to a 1 liter of solution of 0.1

M CH3COO–, how many mole of H+ ions will be there
24. What is the pOH value of a 0.01 M 2-methylpropanoic in the solution? (ignore volume change after mixing)
acid solution? (Ka = 1.6 . 10–5)

31. Draw the molecular structures of the esters that are

25. How many moles of 2-chloroacetic acid are there in 5
formed after the reaction between ethyl alcohol and:
liters of a solution with a pH value of 2?
a. Acetic acid
(Ka = 1.4 · 10–3)
b. Isobutyric acid
c. p-methylbenzoic acid
d. Oxalic acid
26. What is the molarity of a 50 ml tartaric acid solution of
which 250 ml of 0.01 M NaOH is required to neutralize it?

32. Complete the reactions below

[O]
27. Determine A, B, C and D. a. (CH3)2CHCH2OH o
CH2 CH2 + HBr o A b. C2H5COOH + Zn o
C2H5OH
A + KCN o B c. HCOOH + CaCO3 o
heat H+
B + HCl o C d. C2H5COOH + C3H7COOH o
H2O
C2H5OH e. C3H7COOH + SOCl2 o
C + PCl5 o D
P
f. (CH3)2CHCOOH + Cl2 o
COOH
28. g. + K o
CH3 CH COOH
COOH
Cl
COOH
Which compound is produced from the reaction of the h. + Ba(OH)2 o
above compound with NaOH? COOH

144 Oxygen And Nitrogen Containing Organic Compounds

33. Write out the reactions of acetic acid with the reagents 38. Starting from n-butyl chloride, obtain pentanoic acid.
given below.
a. Ba b. Mg(OH)2 c. KHCO3
d. CaCO3 e. C2H5OH / H+ f. SOCl2
g. PCl3 h. PCl5 i. Cl2/P 39. Starting from ethyl alcohol, show how the following two
acids could be produced;
a. Ethanoic acid
b. Propanoic acid
34. Write out the reactions of benzoic acid with the given Show all steps of the reactions.
reagents.
a. Na b. Ca c. CH3OH d. Br2/P e. PCl5 f. SOCl2

40. Complete the following reactions.

35. What is the molecular formula of the magnesium salt of O

a carboxylic acid that contains 9.03% Mg, 63.16% C, C O CH3 +
H
3.76% H and 24.06% O by mass? a. + 2H2O
C O CH3
(Mg : 24 g/mol, C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)
O
+
H
b. C2H5COOH + C2H5OH

36. Write the names of carboxylic acid derivatives given

below.
a. CH3COCl b. CH3CH2COOCH3
c. (CH3COO)2Ca d. (HCOO)2Mg 41. Write out and complete the reactions given below.
e. CH3CONO2 f. Ca(HCOO)2 a. benzoyl chloride + sodium hydroxide
b. acetyl propionate + potassium hydroxide
c. sodium acetate + hydrogen bromide
d. formic acid + phosphorous pentachloride
37. Write molecular formulae of given compounds.
a. Propanoyl chloride
b. Sodium benzoate
c. Ethyl butyrate
d. Magnesium oxalate 42. How can formic acid be separated from a mixture of
e. Sodium acetate formic acid and water? (b.p. of formic acid : 100.5°C
f. Calcium glycolate and b.p. of water : 100°C)
g. Dichloroacetic acid
h. Zinc stearate
i. Acetic acid anhydride
j. Potassium ethanoate 43. Formic acid undergoes a reaction with Fehling’s solution
k. Calcium oxalate whereas acetic acid and propanedioic acid do not.
l. Potassium acrylate Explain.

Carboxylic Acids 145

44. Complete and balance the reactions below. 51. 160 grams of a 20% by mass NaOH solution is used to
neutralize 41 grams of a formic acid - acetic acid mix-
a. HCOOH + Ag+ + OH– o ture. How many moles of acetic acid are present in this
H2SO4 mixture?
b. HCOOH o
Cu, Ni
c. HCOOH o
d. HCOOH + KMnO4 + H2SO4 o
52. How many milliliters of CO2 at STP are produced by
pouring 120 grams of 7% by mass vinegar acid onto a
45. How many grams of 40% by mass formic acid solution bench made of marble?
must be used to precipitate 32.4 grams of Ag from an
excess of Tollens’ reagent?

46. How many grams of Cu2O can be precipitated from the 53. Write
reaction of 150 grams of a 23% by mass solution of a. The molecular formula,
formic acid with an excess amount of Fehling's solution? b. The IUPAC name
(Cu : 63.5 g/mol, O : 16 g/mol) of oxalic acid.

47. Crystalline acetic acid melts below its given melting

point when kept in air. Why?
54. What are fatty acids? Why are they called fatty acids?
Explain.
48. For acetic acid (Ka = 1.8 · 10–5)
a. What is the percentage ionization of a 0.2 M solu-
tion?
b. What is the pH ratio of a 0.2 M solution to a 1.0 M
solution? 55. Which of the following compounds are fatty acids?
a. CH3COOH b. C2H5COOH
c. C3H7COOH d. C15H31COOH
49. 5.6 L of H2 at STP is produced by the reaction of Zn
e. C15C29COOH f. C12H25COOH
metal with a 25% by mass CH3COOH solution with a
density of 1.035 g/mL. What is the volume of this solu-
tion?
(CH3COOH : 60 g/mol)
56. For tartaric acid (grape acid), give
a. Its molecular formula
50. For 220 g of a formic acid-acetic acid - water mixture
b. The functional groups within the molecule
I. 42.56 L H2 at STP is produced by the reaction with
c. Its neutralization reaction with NaOH
an excess amount of Mg
II. 216 g of Ag is precipitated by the reaction with an
excess of Tollens' reagent
what is the mass of water in the mixture?
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol) 57. Give the sources of fatty acids.

146 Oxygen And Nitrogen Containing Organic Compounds

1. What is the molecular formula of the carboxylic acid that 4. 2 methyl, 1 carboxyl and 1 hydroxy group are attached
contains 40.68% C, 54.24 % O and 5.06 % H by mass? to a carbon atom. What is the correct name of this com-
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol) pound?

A) HCOOH B) CH3COOH A) 2,2-dimethyl-2-hydroxyethanoic acid

B) 2-hydroxy-2-methylpropanoic acid

C) COOH D) HOOC(CH2)2COOH C) 1-methyl-1-hydroxybutanoic acid

COOH
D) Isopropionic acid
E) C6H5OH E) 2-hydroxy-3-methylpropanoic acid

2. Which one of the given compounds is a ketoacid?

A) HO C O B) HO C O

OH H

O O O
5. HCOOH(l)
HCOO–(aq) + H+(aq) Ka = 10–4
C) CH3 C C OH D) HO C O CH3 What is the pH of a 10–2 M HCOOH solution?

O A) 2 B) 3 C) 4 D) 5 E) 6
E) H2N CH2 C OH

3. CH3 CH CH CH C O
6. Which of the compounds below has the highest boiling
CH3 NH2 OH OH
point?
What is the correct name of the above compound?
A) CH3CH2CH2CH3
A) 1,2-dihydroxy-3-amino-4-methylpentanol
B) CH3COOH
B) 2-hydroxy-3-amino-4-methylpentanoic acid
C) CH3CH2OH
C) 1-hydroxy-2-amino-3-methylbutanoic acid
D) 1,2-dihydroxy-3-amino-4-methylpentanoic acid D) HOOC CH2CH2 COOH

E) 2-hydroxy-3-amino-4-methylpentanol E) CH3CH2 O CH3

Carboxylic Acids 147

7. 10. What is the molar mass of the aldehyde that is produced
I. CH3 (CH2)3 CH3
by the one-step reduction of a monocarboxylic acid with a
O
molar mass of 74 grams?
II. CH3 (CH2)2 C H
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)
III. CH3 (CH2)3 OH
A) 46 B) 58 C) 62 D) 66 E) 72
O
IV. CH3 (CH2)2 C OH

What is the correct order of boiling points for the above

compounds?
A) I > II > III > IV B) IV > III > II >I
C) I > II = III > IV D) IV = III = II >I
E) IV > II = III > I
11. COOH COONa
+ 2NaOH ¾® + 2H2O
COOH COONa

According to above reaction, how many grams of NaOH

8. CH3 CH C O 1 mol of this compound;
would react with 90 grams of a 20% by mass oxalic acid
OH OH solution?
I. reacts with 2 mol Na (C: 12 g/mol, H: 1 g/mol, O: 16 g/mol, Na: 23 g/mol)
II. reacts with 1 mol NaOH
A) 4 B) 8 C) 16 D) 20 E) 40
III. reacts with 1 mol Zn
which of the above are correct?

A) I only B) III only C) I and II

D) II and III E) I, II and III

12. Which one of the following compounds does not show

9. H C O reacts with;
acidic properties?
OH
OH
I. ammoniacal AgNO3 A) CH2 C O B)
II. NaOH Cl H
III. hydrogen
C) CH2 C O D) COOH
which of the above is/are correct?
OH OH COOH
A) I only B) II only C) I and II
E) HO C O
D) II and III E) I, II and III
OH

148 Oxygen And Nitrogen Containing Organic Compounds

13. Which one of the following compounds is produced by 16. I. C2H5OH + CH3OH o C2H5OCH3 + H2O
the two degree reduction of formic acid? II. CH3OH + CH3COOH o CH3COOCH3 + H2O
A) Methanoic acid B) Methanal C) Methanol III. KOH + HCOOH o HCOOK + H2O
D) Formaldehyde E) Ethyl alcohol Which of the above reactions are esterification reac-
tions?

A) I only B) II only C) I and II

D) II and III E) I, II and III

17. O
O O I. H C OH
14. Regarding HO C CH2 C CH3 , O
II. HO C OH
I. it is a dicarboxylic acid.
O O
II. when it is oxidized, an ether is formed.
III. HO C C OH
III. it is an acid anhydride.
Which of the above statements is/are incorrect? Which of the above compounds show both acid and
aldehyde properties?
A) I only B) II only C) I and III
D) II and III E) I, II and III A) I only B) III only C) I and II
D) II and III E) I, II and III

18. Which one of the following is the product of the reaction

between dilute H2SO4 and formic acid?

15. What is the molar mass of the ester that is produced A) CH3 C O B) CH3 CH2OH
from the reaction of 60 grams of a carboxylic acid with H
46 grams of an alcohol?
C) CO + H2O D) CO2 + H2O
A) 106 B) 88 C) 98 D) 124 E) 82
E) CO + CO2 + H2O

Carboxylic Acids 149

19. Which one of the following compounds cannot be oxi- 23. I. Acetic acid
dized to a carboxylic acid? II. Lactic acid
III. Oxalic acid
A) Methanol B) Ethanol C) Butanol
Which of the above represent a hydroxy acid?
D) n-propanol E) 2-pentanol
A) I only B) II only C) III only
D) II and III E) I, II and III

20. Which one of the following carboxylic acids cannot be

obtained by the reaction of a Grignard compound with
CO2?
A) HCOOH B) CH3COOH C) C2H5COOH
D) C3H6COOH E) C4H10COOH
24. Some common acids found in daily life together with their
sources are given below,
I. lemon salt: citric acid
II. aspirin: acetyl salicylic acid
III. vinegar: acetic acid
21. 134.4 mL CO2 at STP is obtained from the reaction of 6 Which pairings are correct?
grams vinegar with an excess of NaHCO3. What is the
A) I only B) I and II C) II and III
mass percentage of acetic acid in the vinegar?
D) I and III E) I, II and III
(CH3COOH : 60 g/mol)

A) 4.5 B) 6.0 C) 9.6 D) 21 E) 45

22. Large molecules of saturated monocarboxylic acids are 25. O C CH CH CH2 C O

solid at room temperature.
OH OH OH H
I. C17H35 COOH The compound above,
II. C15H31COOH I. is optically active
III. C17H33 COOH II. contains four asymmetric carbon atoms
Which of the above compounds are solid at room con- III. contains aldehyde, alcohol and carboxyl groups
ditions? Which of the above are correct?

A) I only B) II only C) I and III

A) I only B) III only C) I and II
D) II and III E) I, II and III
D) II and III E) I, II and III

150 Oxygen And Nitrogen Containing Organic Compounds

26. CH3 CH COOH 28. HO OH
OH C C

Regarding above compound, O C CH CH CH2 OH

O
I. it reacts with KOH OH

II. it is optically active How many asymmetric carbon atoms does this com-
III. H2 gas is evolved upon reaction with Mg pound have?
Which of the above statements are correct? A) 0 B) 1 C) 2 D) 3 E) 4

A) I only B) II only C) I and II

D) I and III E) I, II and III

29. H2C CH COOH

NH2 OH

27. In digital clocks, a liquid crystal substance which is The above compound,
I. resistant to acids and bases I. has 2 asymmetric carbon atoms.
II. optically active II. is optically active.
is needed. III. has 2 optical isomers.
Which one of compounds below satisfies these two con- Which of the above statements is(are) wrong?
ditions?
A) I only B) III only C) I and II

A) CH3CH2 CH CH2 CN D) II and III E) I, II and III

CH3

O
B) CH3CH2 CH O C

CH3 O CH3

O
C) CH3 CH O C
30. I. Naturally occurring fatty acids exist in the cis-geom-
CH3 O CH3
etry.
II. The simplest fatty acid is butyric acid, C3H7COOH.
D) CH3 O CH2 CH CH3 III. Double bonds in the structure decreases the melting
CH3 points of fatty acids.
Which of the above statements is(are) true?
E) CH3 CH2 CH CH2 CH3
A) I only B) II only C) I and III
CH3
D) II and III E) I, II and III

Carboxylic Acids 151

 DOUBLE PUZZLE
These words have been jumbled up (there are no letters missing). Luckily, clues have been left. Put the correct spelling in the
Answer Grid. Transfer the numbered letters to the reference check, and use this to fill in the SECRET MESSAGE.

ANSWER GRID MIXED LETTERS CLUES

7 Compounds that contain carboxyl
1 BYACRXOIDLCCISA
groups are called _____________
These compounds may be prepared
21 11
2 SACICLODIXRCBAY by the oxidation of aldehydes or
primary alcohols
13
A group that is formed by the combination
3 PROXYUGLCRBOA of carbonyl and hydroxyl groups is called
the _____________ group.
3
4 OPARICPODICAN Three carbon containing carboxylic acid.

8 The carboxylic acids that contain a

5 XOYDACIYHDR
hydroxyl group are called _____________

16 The carboxylic acids that contain an amino

6 NAMIDOACIS
group (–NH2) are called _____________

9 Common name of methanoic acid.

7 MODCACFIRI
It is obtained from ants.

4
8 TACECIDCAI This acid is also known as vinegar acid.

18
9 IDOXLACACI It is the strongest of the dicarboxylic acids.

5 Lemon contains _____________ which

10 DRCITICACI
is also known as lemon acid.

11 19 Carboxylic acids react with alcohols to

STERES
produce these compounds

REFERENCE CHECK
A B C D E F G H I J K L M N O P Q R S T U V W X Y Z
23 10

SECRET MESSAGE
9 16 8 21 13 7 11 18 3 9 16 9 3 5 19

16 8 4 10 4 16 23 16 9 3 5 19

152 Oxygen And Nitrogen Containing Organic Compounds

 INTRODUCTION
The reaction between an acid and a base is called neutralization and the prod-
ucts are salt and water. The parallel reaction between a carboxylic acid and an
Esterification alcohol is called esterification and the products are an ester and water.
To identify the bond breakages in ester-
O O
ification, an alcohol containing the 18O H+
isotope is used. After esterification it is R C OH + HO R¢ R C OR¢ + H2O
seen that the 18O isotope appears in carboxylic alcohol ester water
acid
the ester. This result reveals that the
water is formed from the hydroxyl Neutralization and esterification reactions are similar in terms of the functional
group of the acid and the hydrogen of
groups of the reactants and products. The main differences between these two
the alcohol. In other words the OR
group from the alcohol molecule reactions are that esterification reactions are slow, reversible and don’t take place
replaces the OH group of the acid between ions.
molecule.
O O 1. ESTERS
18 18
R C OH + H O R R C O R + H2 O
carboxylic alcohol ester water Esters are derivatives of carboxylic acids formed by replacing the hydroxyl
acid
( OH) group by an alkoxy ( ORc) group. They can be defined as alkyl salts
of carboxylic acids and are represented by the general formula RCOORc.

O O
R C R C
O R¢ O R¢
the hydroxyl group of the carboxylic esters are alkyl salts of
acid is replaced by an alkoxy group carboxylic acids

O
The functional group of esters, C O , is bonded to two alkyl groups,
except for formates, which have a hydrogen atom bonded to the carbon atom of
the functional group.

O O
H C R C
O R O R¢
The ester derived from Esters derived from the other
formic acid has one H atom bonded acids have an alkyl group bonded
to the C atom of the functional group. to the C atom of the functional group.

2. NOMENCLATURE OF ESTERS
The nomenclature of esters is similar to the nomenclature of the carboxylic acid
salts. The alkyl group bonded to the oxygen atom is named first, then the –ic acid
ending of the corresponding carboxylic acid is changed to –oate.

154 Oxygen And Nitrogen Containing Organic Compounds

 O O O Formula
Common IUPAC
Name Name
H C O CH3 CH3 C O CH3 C 2H5 C O C2 H 5
O Alkanoyl
methyl methanoate methyl ethanoate ethyl propanoate Acid halide
methyl formate methyl acetate ethyl propionate R C X halide
O O Acid anhy- Alkanoic
O O R C O C R dride anhydride

C O CH3 CH3 C O CH CH2 O

Ester Alkanoate
ethenyl ethanoate R C O R¢
methyl benzoate vinyl acetate
O
Amide Alkanamide
R C NH2

Table 1: Some carboxylic acid derivatives

Common Naming
The "ester" suffix is added to the end of alkyl groups found in an ester. The alkyl
name from the alkoxy group is put first.

O O O

H C O CH3 H3C C O CH3 H3C C O C2 H 5

methyl ester dimethyl ester ethyl methyl ester

1
Name of the following compounds:
O O

a. CH3 C O CH CH3 b. CH3 CH2 O C CH Cl

CH3 Cl
O O CH3
c. CH2 O C H d. Cl C O C CH3
CH3

a. Isopropyl ethanoate
b. Ethyl dichloroethanoate
c. Benzyl methanoate
d. t – butyl – p – chlorobenzoate

Esters 155
 2
Write the structural formulae for the following esters.
a. Isobutyl acetate b. Ethyl benzoate
c. t–butyl formate d. p–chlorophenyl–2–methyl butanoate
e. Ethyl bromoethanoate f. Sodium ethanoate
g. Ethyl propanoate h. Benzyl acetate

O O
a. CH3 C O CH2 CH CH3 b. C O CH2 CH3

CH3

O CH3 O
c. H C O C CH3 d. Cl O C CH CH2 CH3

CH3 CH3

O O
e. CH2 C O CH2 CH3 f. CH3 C ONa

Br
O O
g. C2H5 C O C2H5 h. CH3 C O CH2

3. PHYSICAL PROPERTIES OF ESTERS

Esters with small chained alkyl groups are colorless liquids with pleasant odors.
They are obtained from natural sources such as plants, flowers and fruits and
are what give them their pleasant smells. So, for example, the smells of mint and
thyme are due to esters in their structures.

Natural fruit aromas are mixtures of certain organic compounds and esters.
Synthetic aromas prepared in laboratories are simple mixtures of these same esters
and organic compounds. They are used in perfumes, foods and drinks to give taste
and pleasant smells. Ethyl acetate, for example, is a colorless liquid with an apple
flavour; it is known as apple ester and is used in perfumery as a fruit essence.
Propyl acetate has the smell of pears, isopentyl acetate that of bananas and ethyl
butyrate smells of pineapples. All are colorless liquids. Higher molar mass esters
are odorless.

156 Oxygen And Nitrogen Containing Organic Compounds

 Name Structure Odor
Isobutyl formate HCOOCH2CH(CH3)2 Raspberry
Ethyl acetate CH3COOC2H5 Apple
Propyl acetate CH3COOC3H7 Pear
Ethyl butyrate C3H7COOC2H5 Pineapple
Isopentyl acetate CH3COOC5H11 Banana
Methyl salicylate HOC6H4COOCH3 Wintergreen
n – pentyl butyrate C3H7COOC5H9 Apricot
n – octyl acetate CH3COOC8H17 Orange

Table 2: How esters smell. The smell of pineapple is due to ethyl

butanoate in its structure.
Esters do not have hydrogen bonding between their molecules and therefore they
have lower boiling points than carboxylic acids of the same molar mass. Low molar
mass esters are liquids with low boiling points. Higher molar mass esters (fats and
waxes) are solids or liquids with a high density. Lower molar mass esters form
hydrogen bonds with water but as the length of their alkyl groups increase, their
solubility in water decreases. Esters which are insoluble in water are soluble in alco-
hol and ether. Esters have lower densities than water.
Liquid esters are good organic solvents, for example, nitrocellulose is used to dis- Isopenthyl acetate gives bananas their
solve some natural and synthetic resins and plastics. pleasant smell.

Name Chemical Formula Melting Point (°C) Boiling Point (°C) Solubility (g/100 mL water)
Methyl formate HCO2CH3 – 99 31.5 30 (very soluble)
Ethyl formate HCO2CH2CH3 – 79 54 10.5
Methyl acetate CH3CO2CH3 – 99 57 24.40
Ethyl acetate CH3CO2CH2CH3 – 84 77 7.90 (25°C)
Propyl acetate CH3CO2CH2CH2CH3 – 93 102 1.89 (moderately soluble)
Butyl acetate CH3CO2CH2(CH2)2CH3 – 74 125 1.00 (22 °C)
Ethyl propanoate CH3CH2CO2CH2CH3 – 73 99 1.75
Ethyl butanoate CH3(CH2)2CO2CH2CH3 – 93 120 0.51
Ethyl pentanoate CH3(CH2)3CO2CH2CH3 – 91 145 0.22
Ethyl hexanoate CH3(CH2)4CO2CH2CH3 – 68 168.0 0.063
Methyl benzoate C6H5CO2CH3 – 12 199 0.15
Ethyl benzoate C6H5CO2CH2CH3 – 35 213 0.08
Methyl salicylate o – HOC6H4CO2CH3 –9 223 0.74 (30°)

Table 3: Physical properties of some esters

Esters 157
 4. CHEMICAL PROPERTIES OF ESTERS
4.1. HYDROLYSIS OF ESTERS
Soap in history An ester hydrolyzed in the presence of an acid catalyst produces a carboxylic acid
and an alcohol. This hydrolysis, the reverse of esterification, is an equilibrium reac-
Soap was first known to be used in 2500
B.C. at Mesopotamia. It was also writ- tion.
ten by the Roman Emperor Julius O O
H+
Caesar that some tribes in ancient R C OR¢ + H OH ƒ R C OH + R¢ OH
Egypt used soaps. ester carboxylic acid alcohol
Soap was produced using the same
O O
method as today, by heating soda or H
+

wood ash with fats. CH3 C O CH3 + H OH CH3 C OH + CH3 OH

methyl acetate acetic acid methyl alcohol

In order to increase the amount of products from the hydrolysis reaction, large
quantities of water are used which shift the equilibrium to the right.

4.2. SAPONIFICATION OF ESTERS

When esters are heated with aqueous solutions of strong bases such as NaOH and
KOH, salts of carboxylic acids are produced which are known as soaps. A side
product of the saponification reaction is an alcohol. The reaction is irreversible.
O O
heat – +
R C OR¢ + NaOH R C O Na + R¢ OH
ester base sodium carboxylate alcohol

O O
heat – +
C3H7 C O C2H5 + NaOH C3H7 C O Na + C2H5OH
ethyl butyrate sodium butyrate ethyl alcohol

4.3. REDUCTION OF ESTERS

Esters can be reduced to alcohols in different ways. During reduction, the acyl
Soaps are salts formed from the reaction
group of an ester is reduced to a primary alcohol. The alkoxy group of an ester
of bases with esters known as fats.
is bonded to hydrogen atom and so depending upon the alkyl group present, the
alkoxy group is converted to a primary, secondary or tertiary alcohol. The most
important reduction techniques are the following.
Esters are reduced by sodium in the presence of ethanol.
O
C2H5OH, Na
R C OR¢ R CH2 OH + R¢ OH
ester primary alcohol alcohol

158 Oxygen And Nitrogen Containing Organic Compounds

 O
C2H5OH, Na
H C OC2H5 CH3 OH + C 2H 5 OH
ethyl methanoate methyl alcohol ethyl alcohol

Esters can also be reduced by the addition of hydrogen in the presence of oxides
of copper and chromium known as copper chromide. Reduction can also be car-
ried out by LiAlH4, though this method is very expensive.

O
CuO – CuCr2O4
R C OR¢ + H2 250 °C, 300 atm
R CH2OH + R¢OH
ester primary alcohol alcohol

O
CuO – CuCr2O4
CH3CH C OCHCH3 + H2 250 °C, 300 atm
CH3CHCH2 OH + CH3CH OH

CH3 CH3 CH3 CH3

isopropyl isobutanoate isobutyl alcohol isopropyl alcohol
(1°) (2°)

The direct reduction of a carboxylic acid to an alcohol is very difficult to carry out,
so the acid can be first esterified and then reduced to the alcohol.

4.4. REACTION WITH AMMONIA

Esters can react with ammonia to form an amide and an alcohol. The acyl group
of the ester bonds to the NH2 group of ammonia to form an amide while the
alkoxy group of the ester is bonded to the H of ammonia to form an alcohol.

O O

R C OR¢ + H NH2 R C NH2 + R¢ OH

ester ammonia amide alcohol

O O

CH3 C OC3H7 + H NH2 CH3 C NH2 + C3H7 OH

propyl acetate ammonia acetamide propyl alcohol

3
Write out the chemical reactions of methyl acetate with the following reagents.
a. H2O b. NaOH
c. NH3 d. H2(CuO and CuCr2O4 catalysts)

Esters 159
 O O
H+
a. CH3 C OCH3 + H2O CH3 C OH + CH3OH
methyl acetate acetic acid methyl alcohol

O O
b. CH3 C OCH3 + NaOH CH3 C ONa + CH3OH
methyl acetate sodium acetate methyl alcohol

O O
c. CH3 C OCH3 + NH3 CH3 C NH2 + CH3OH
methyl acetate acetamide methyl alcohol

O
CuO and CuCr2O4
d. CH3 C OCH3 + H2 CH3CH2OH + CH3OH
methyl acetate ethyl alcohol methyl alcohol

5. PREPARATION OF ESTERS
Esters can be produced synthetically for use in perfumes and synthetic flavour-
ings.

5.1. FROM CARBOXYLIC ACID AND ALCOHOLS

Carboxylic acids react with alcohols to form esters in the presence of an acid cat-
alyst. In the esterification reaction OH is removed from the acid and H
removed from the alcohol to form water. Such reactions are equilibrium reac-
tions and are very slow.
O O
H+
R C OH + HO R¢ R C OR¢ + H2O
carboxylic alcohol ester water
acid

The yield of an esterification reaction is low. There are large amounts of acid and
alcohol left in the reaction mixture. The use of an excess of either the carboxylic
acid or the alcohol increases the yield. The yield of an esterification reaction can
Perfumes contain esters. also be increased by removing water from the reaction mixture as is formed.

4
What is the molar mass and possible formula of the ester that is formed from a
monocarboxylic acid with molar mass 60 g/mol and a monoalcohol with molar
mass 46 g/mol? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

160 Oxygen And Nitrogen Containing Organic Compounds

 acid + alcohol o ester + water
– 1 mol – 1 mol + 1 mol + 1 mol
60 g 46 g x + 18 g
According to the law of conservation of mass: 60 + 46 = x + 18
molar mass of the ester (RCOORc) = 88 g/mol.
RCOORc = 88 g/mol
R + Rc + 12 + 16 + 16 = 88 g
R + Rc = 44 g
So, possible
R = CH3 = 15 g/mol
Rc = C2H5 = 29 g/mol
When R : H or CH3 or C2H5
Rc : C3H7 or C2H5 or CH3
If we check the molar masses of the acid and alcohol, the correct formulae of
the acid and alcohol are CH3COOH and C2H5OH respectively. So the structural
formula of ester is
O

CH3 C OC2H5

5.2. FROM CARBOXYLIC ACID DERIVATIVES

Acid anhydrides and acid chlorides react with alcohols to produce esters.

O O

R C Cl + HOR¢ R COR¢ + HCl

O O O

R C O C R + R¢ OH R C OR¢ + RCOOH

Examples;

O O

C2H5 C Cl + HO C3H7 C2H5 C OC3H7 + HCl

propyl chloride propyl propanote

O O O
CH3 C O C CH3 + HO CH3 CH3 C OCH3 + CH3COOH
acetic anhydride methyl acetate

Esters 161
 5
Write the complete reactions between the following pairs of compounds and
name the products.
a. propyl alcohol – butyric acid
b. acetic anhydride – allyl alcohol
c. propanoyl chloride – ethyl alcohol

a. C3H7OH + C3H7COOH C3H7COOC3H7 + H2 O

propyl alcohol butyric acid propyl butyrate water

CH3C O
b. O + CH2 CHCH2OH CH3COOH + CH3COOCH2CH CH2
CH3C O allyl alcohol acetic acid allyl acetate
acetic anhydride

c. C2H5COCl + C2H5OH C2H5COOC2H5 + HCl

propanoyl chloride ethyl alcohol ethyl propanoate hydrochloric acid

6. FATS
Fats are esters of fatty acids and glycerine. They are also known as triglycerides.
Fatty acids are long, straight chained carboxylic acids and glycerine is a trialcohol.
Fats are formed by replacing the hydrogen atoms in the hydroxyl groups of glyc-
erine with acyl groups of fatty acids.
O O

HO C R CH2 O C R
CH2 OH O O
Fat Facts
CH OH + HO C R CH O C R + 3H2O
Fats play an important role in nutri-
O O
tion. Occuring naturally in foods; fats CH2 OH
and oils are a concentrated form of HO C R CH2 O C R
energy for the body. As well as storing glycerol (glycerine) fatty acid glyceride (fat)
energy in the body, fats are used to
insulate body tissues and help trans- Fatty acids may form mono, di– or tri– glycerides with glycerine as, one or two
port fat soluble vitamins throughout of the –OH groups in glycerine may not react with the fatty acid.
the blood. An important role of fats is
CH2 COOR CH2 COOR CH2 COOR
in food preparation , they enhance
food flavor, add texture, make baked CH OH CH COOR¢ CH COOR¢
products tender, and conduct heat dur-
CH2 OH CH2 OH CH2 COOR¢¢
ing cooking.
monoglyceride diglyceride triglyceride

162 Oxygen And Nitrogen Containing Organic Compounds

If the connecting fatty acids to glycerine are all the same, the glyceride known as
simple, if the acids are different, it is known as complex .

O O
Cholesterol
CH2 O C C17H33 CH2 O C C17H35
O O Is cholesterol dangerous for our body,
is it good or bad for us?
CH O C C17H33 CH O C C17H31
Chemically a lipid, cholesterol is an
O O
important constituent of body cells.
CH2 O C C17H33 CH2 O C C17H33 This fatty substance, produced mostly
triglyceride 1 – stearo – 2 – palmito – 3 – oleo glyceride in the liver, is involved in salt forma-
(simple glyceride) (complex glyceride) tion and in the transport of fats in the
blood stream to tissues throughout the
Pure fats consist of around 95% by mass triglyceride. The remaining 5% consists body.
of mono and diglycerides, glycerine, some free fatty acids, vitamins dissolved in Every cell of the body contains choles-
the fat, and minerals that give color and taste. Thus fats do not have a fixed melt- terol, it is a waxy, fat-like substance. In
ing point. the body cholesterol carries out many
important functions such as strength-
ening cell membranes, helping digest
6.1. CLASSIFICATION OF FATS
fats and making hormones. On the
Vegetable fats: other hand, high levels of cholesterol
These are largely stored in the seeds of vegetables. Olive, corn, cotton, sunflower, can be dangerous for the body. When
level of blood cholesterol rises, it can
soybean, sesame, peanut, hazelnut, dates, almonds and coconuts are the main
build up on artery walls increasing the
sources of vegetable oils.
risk of blood clots, heart attacks and
Animal fats: strokes.
Sheep, cow and fish are the main source of animal fats. Suet and fish oil are the
most common animal fats. They may be either solid or liquid, the same as veg-
etable fats.

According to Their Physical State

Fats and oils, since they are mixtures, may be solid, liquid
or halfway in between depending upon the amount of glyc-
erides they contain. For example, suet which contains a
high amount of tri–stearine is solid, but olive oil which con-
tains a high amount of glycerine is liquid. Butter and mar-
garine are half–solid as they are mixtures of both solid and
liquid glycerides.

Some fatty acids are solid due to saturation. An example is

coconut oil which is solid because it contains mainly tri-
palmitin and tristearine glycerides. Palmitic acid and stearic Olive oil is one of
the most important
acid are saturated carboxylic acids.
vegetable oils Corn, a very important source of oil.

Esters 163
Some of examples oil with their sources.

If the fatty acids that form the fats and oils are unsaturated, the fats tend to
be liquids. Liquid oils are unsaturated, the number of double bonds in the
fatty acids decreases the freezing point of the fat or oil.

7. HYDROGENATION AND MARGARINES

As stated above, an oil is unsaturated if the fatty acids contain double bonds.
Liquid oils can be hydrogenated, using a nickel catalyst in the saturation process
and turned into solid such as margarines.

O O

H2C O C C17H33 H2C O C C17H35

O O
Ni
HC O C C17H33 + 3H2 pressure heat HC O C C17H35
O O

H2C O C C17H33 H2C O C C17H35

liquid oil unsaturated solid oil saturated
hydrocarbon hydrocarbon
chains chains

In the production of margarines, sunflower, corn, cotton, sesame, soybean and

even fish oil can be used as a starting material.

164 Oxygen And Nitrogen Containing Organic Compounds

Some liquid oils cannot be saturated completely and a semi–solid oil is obtained.
The hydrogenation process also gets rid of smelling substances from the fat or
oil. Margarines are then made ready for consumption by the addition of coloring,
flavoring, salt, milk and butter.

Margarines are less preferable than oils for good health. Since the melting points
of margarines are higher than that of human body temperature, they may cause
some coronary diseases.

8. SAPONIFICATION
Hydrolysis of glycerides (fats) in a basic medium produces glycerol (glycerine)
and a mixture of salts of long chained carboxylic acids (fatty acids).
O O

CH2 O C R NaOH Na+O– C R

O CH2 OH O
heat
CH O C R + NaOH CH OH + Na+O– C R
O O
CH2 OH
NaOH + –
CH2 O C R Na O C R
glyceride (fat) glycerine sodium salts of fatty acids

Fats, when heated with a solution of NaOH or KOH are hydrolyzed. After the
hydrolysis, glycerine and long chained carboxylic acids salts are left, this mixture
is soap and the process is called saponification. Soaps are basic salts which are
formed by weak fatty acids and strong bases. For this reason, soap solutions
show basic properties. Saponification is the reverse process of esterification.

H H H H H H H H H H H H H H H H H O H H H H H H H H H H H H H H H H H O
+ +
H C C C C C C C C C C C C C C C C C C Na H C C C C C C C C C C C C C C C C C C K
– –
H H H H H H H H H H H H H H H H H O H H H H H H H H H H H H H H H H H O

– +
C17H35COO Na Sodium stearate C17H35COO– K+ Potassium stearate

When NaOH is used in the saponification process, a solid soap is produced but
when KOH is used, a molten soft soap is produced.

Esters 165

A drop of water on a hydrophobic (water
hating) surface. Thus, water is ineffective
getting rid of dirt.
Soap micelles absorb grease molecules
into their interiors so that the grease is
suspended in the water and can be
washed away.
9. CLEANING PROCESS OF SOAPS
Water soluble stains on the surface of clothes can easily be cleaned using water.
If our hands get covered in salt, for example, it is enough to wash them with plen-
ty of water. However, water isn’t so effective at getting rid of oily stains.
Most dirt particles (on the surface of clothes, on the skin etc.) become surround-
ed by a layer of oil or fat. Water molecules alone are unable to get rid of this kind
of dirt because they cannot penetrate the oily layer. Soap must be used to dis-
perse this kind of dirt.
The chemical structure of soap explains its cleaning ability. There are two main
parts of a soap’s structure. Soap molecules contain a nonpolar alkyl tail and a
polar head that can interact with the polar water molecules. A soap solution is
not a true solution, it doesn’t have individual fatty acid anions in the water, but
rather groups of these ions called micelles.
Soaps clean oily stains by taking the oil molecules into the nonpolar interior of
the micelles which are then carried away by the water. The hydrophobic (water
hating) end of a soap molecule can dissolve in an oily stain.
Soaps that are used for cleaning are sodium and potassium soaps. The Ca+2
and Mg+2 salts of fatty acids are insoluble in water, these salts are known as mar-
ble salts.
Soap anions form precipitates with the cations in hard water, i.e, Ca+2 and Mg+2 ,
and this reduces their cleaning ability, prevent this water may be softened with
slaked lime.
Magnesium oleate is insoluble in water and soluble in organic solvents, hence it
can be used for dry cleaning.
Lead stearate is used in the production of salve.
Aluminium stearate is used in the manufacture of water-resistant clothes.

Hydrophilic head (a) (b) (c) Soap molecule

H
O H
Hydrophobic tail O
H H

Water H2 O
Oil

a. The tail part of the soap, which is hydrophobic (water hating) dissolves in the oily stain.
b. Soap molecules then move between the oil and the surface, surrounding the oil stain.
c. The water dissolves the heads of the soap molecules and lifts the oil from the surface.

166 Oxygen And Nitrogen Containing Organic Compounds

10. DETERGENTS
Detergents are artificial soaps. Their structure is similar to that of soaps; any mol-
ecule having nonpolar and polar sections similar to those in soap molecules may
disperse oily stains on clothes, hence detergents too have a hydrophobic and
hydrophilic end.

Detergents in which the hydrophilic group is an anion are called anionic deter-
gents. The most common of these are the alkyl benzene sulfanates (ABS) and
alkyl sulfates.

These are produced by hydrolyzing the bisulfate salts of long chained alcohols
with sodium hydroxide.
Magnesium oleate is insoluble in water.
C12H25 OH + H2SO4 o C12H25 OSO3H + H2O
dodecyl alcohol dodecyl bisulfate

– +
C12H25 OSO3H + NaOH o C12H25 OSO3 Na + H2O
dodecyl bisulfite sodium dodecyl sulfate

Alkyl sulfate detergents are known as AS detergents, an example of the struc-

ture of this type is,
–
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3 Na+
sodium dodecyl sulfate

Most detergents contain the benzene ring in their structure. These kind of deter-
gents are called ABS detergents, as mentioned above.

Synthetic detergents are more

active cleaners than soaps. They
don’t form precipitates with Ca+2
and Mg+2 ions in hard water and
are therefore more effective
cleaners in hard water than
soaps.

The cleaning mechanism of syn-

thetic detergents is similar to that
of soaps. Na2CO3, Na3PO4 and
other basic additives are added to
detergents to make their solutions
basic so that they are not Detergents are not decomposed into
hydrolyzed in solution. This is simpler substances by microorganisms,
necessary as detergents do not therefore when detergents get into
have a basic character like soaps. rivers, lakes and ground water, they
become an environmental problem.

Esters 167
1. What does “derivative of carboxylic acid” mean? Explain O
with examples.
d. CH2 CH2 O C H

Br

2. What is an ester? Define. H CH3

e. C C
H3C O C O

3. CH3
a
O
CH3 C c H3C
b
O CH3 f. CH CH2 C O
H3C O CH3
What are the approximate values of the angles a, b and c?

O
C O C3H7
4. Which of the following compounds are esters? g.
C O C3H7
O CH3
O
a. CH3 CH2 C O C CH3
H3C O
CH3
O h. CH O C H

b. CH3 C CH2 O CH3 H3C

O O
c. CH3 CH2 C OH i. C O CH2
O Cl
d. C OCH3

6. Write out the molecular formulae for compounds

below.
5. Name the compounds below. a. methyl acetate
O b. isobutyl propanoate
a. CH3 C O CH3 c. phenyl methanoate
d. propyl butanoate
O
e. ethyl butyl ester
b. H C O CH3
f. ethyl propanoate
O g. potassium stearate
c. CH3 C O h. t–butyl ester
i. ethyl methanoate

168 Oxygen And Nitrogen Containing Organic Compounds

 j. methyl dichloroethanoate 11. Write out the reduction products of the given esters.
k. t–butyl benzoate Which one of the esters has reduction products that are
l. methyl propanoate all primary alcohols?
m. diethyl ester O
n. neopentyl formate a. H C OCH3
o. butyl ester of acetic acid
O
p. ethyl ester of formic acid
b. CH3 C O CH CH3
r. ethyl ester of E–methyl butyric acid
CH3
s. o–hydroxyphenylmethyl propanoate
O
c. CH3 CH C OCH3
CH3
7. Write the substances formed by the hydrolysis of the CH3 O
given compound.
d. CH3 C C OCH3
O
CH3
CH3 C O

8. Both compounds given below are cycloesters.

What are the products formed by the hydrolysis of these
compounds?
O
O O
a. O b. O 12. Write out the following reactions of H C OC3H7

a. hydrolysis with H2O

b. with KOH
c. with Na in the presence of alcohol

9. Which compounds are produced by the reduction and

the hydrolysis of the given compound?
O
CH3 C O CH CH3

CH3
O

13. For C15H31 C OC4H9 ,

write out the following reactions and name the products.

10. What is meant by the saponification of esters? Give the a. hydrolysis by H2O
differences between saponification and hydrolysis? b. saponification with NaOH

Esters 169
14. Write the molecular formulae of the esters produced by 18. What is the molar mass of the ester that is produced by
the acids and alcohols given below. the reaction between oxalic acid and an excess amount
of methanol?
a. acetic acid– n – propanol
b. acetic acid–isobutyl alcohol
c. formic acid–benzyl alcohol
d. benzoic acid–methanol
19. The molar mass of an ester produced by ethanol and a
e. formic acid–methanol
dicarboxylic acid is 174 g/mol. What is the molecular
f. butyric acid–propyl alcohol formula of the carboxylic acid?

O
15. Complete the following reactions and name the prod- C2H5 C O
20. Write down how may be
ucts. formed from;
a. C3H7COOH + CH3COCl o
a. a carboxylic acid and an alcohol
b. CH3 – COCl + (CH3)3COH o
b. an acid anhydride and an alcohol
c. (COONa)2 + CH3CHBrCH2CH3 o
c. an acid chloride and an alcohol

21. Explain the following terms.

a. fat b. glyceride
16. What is the molecular formula of the ester that is pro-
duced by the reaction between a carboxylic acid of c. monoglyceride d. diglyceride
molar mass 60 g/mol and an alcohol of molar mass 60 e. triglyceride f. simple glyceride
g/mol? g. complex glyceride h. hydrophobic
i. hydrophilic

22. What are the factors affecting the physical states of fats?
17. Monocarboxylic Acid Monoalcohol
——————————— —————————
I. 60 g/mol 60 g/mol
II. 60 g/mol 46 g/mol
III. 46 g/mol 32 g/mol 23. How many grams of 70% by mass NaOH solution is
needed to neutralize 218.4 grams of a diglyceride of
Find the molar masses of the esters which are formed by
molar mass 624 g/mol?
the reaction is between the alcohols and acids given
above? (H2O : 18 g/mol)

170 Oxygen And Nitrogen Containing Organic Compounds

24. What is margarine? How is it produced? 30. Match up the types of reactions.
a. chlorination of methane I. Esterification
b. production of ethyl II. Hydrolysis
alcohol from ethyl
methyl ether
c. production of solid fats III. Reduction
25. How many grams of glycerine are needed to produce tri- from liquid fats
oleo glyceride from 16,92 grams of oleic acid?
d. production of wax from IV. Saponification
palmitic acid and alco-
hol?
e. production of ethanol V. Substitution reaction
and ethanoic acid from
ethyl ethanoate
26. Write the products for the given fat after;
f. production of glycerine
O O and potassium palmi- VI. Hydrogenation
CH3(CH2)14 C O CH2 CH CH2 O C (CH2)12 CH3 tate from glyceryl tri-
palmitate and KOH
O C (CH2)10CH3

a. hydrolysis by water 31. Give the chemical definition of soap and explain what
b. reaction with KOH sodium soaps, potassium soaps and ammoniacal soaps
Name the type of reaction. are.

32. Why don’t soaps foam in hard water?

33. What is the contribution of the basicity of soaps to their

27. Write out the reactions of trioleo glyceride
cleaning effect ?
(C3H5(C17H33COO)3) with;

a. NaOH solution at high temperatures

b. H2O vapor in an acidic medium 34. What is a detergent? What are their chemical properties?

35. What are the similarities and differences between soaps

and detergents?

28. What is wax? How is it produced?

36. What are the factors that make detergents better clean-
ing agents than soaps?

37. What do AS, ABS and LAB stand for?

29. What are the differences between wax, fat, butter and What are the effect of these substances on the environ-
mineral oil (hydraulic oil)? ment?

Esters 171
1. Esters are; 5. O
I. Alkyl salts of carboxylic acids
CH2 CH2 C O CH2 CH2 CH CH3
II. Formed by the attachment of an alkoxy group to an
Cl CH3
acyl group
III. Oxidation products of carboxylic acids What is the correct name for the compound above ?
Which of the above statements, is(are) correct?
A) Isopentyl ester of E–chloroacetic acid
A) I only B) I and II C) III only B) Pentyl ester of D–chloroacetic acid
D) II and III E) I, II and III C) E–chloro ethyl ester of isovaleric acid
D) Isopentyl ester of E–chloropropionic acid
E) 2–chloropropionic acid

2. Which one of the following groups cannot be attached

to the carbon of the functional group of an ester of
molar mass 102 g/mol?

A) H– B) CH3– C) C2H5– D) C3H7– E) C4H9– 6. Compounds formed by the reaction of inorganic or

organic acids with alcohols are called esters.
According to this, which one of the given compounds is
not an ester?
O
A) HCOOCH3 B) C4H9 C OCH3
3. Which one of the following compounds does not contain
an acyl group? C) CH3 C O D) CH2ONO2
O C2 H 5 CH2
A) Ketones B) Esters C) Carboxylic acids
D) Amides E) Ethers CH2ONO2
E) CH2 CH CH2
OH OH OCH3

4. I. Formic acid
II. Acetic acid
III. Propionic acid
7. What is the name of CH3COOCH3 ?
Which of the above acids does not have an ester iso-
mer? A) Methyl methanoate B) Ethyl methanoate
A) I only B) II only C) I and II C) Ethyl acetate D) Methyl acetate
D) II and III E) I, II and III E) Methyl formate

172 Oxygen And Nitrogen Containing Organic Compounds

8. Which one of the compounds shown below is iso- 11. O
propyl–p–methyl benzoate?
I. CH3 C OCH2CHCH3

CH3
A) OCH2CH2CH3
O

CH3 II. CH3 C CH2 O CH3

O
B) H3C COOCH2CH2CH3
III. CH3 CH2 O C

C) H3C COOCHCH3
IV. CH3 CH2 O CH3
CH3

D) H3C COOCHCH3
Which of the compounds shown above can be
hydrolyzed with an acid catalyst?
CH3

CH3 A) I only B) I and II C) I and III

E) H3C COOCCH3 D) III only E) IV only

CH3

12. What is the type of reaction occurring when isobutyl

acetate reacts with NaOH?
9. Which of the given pairs of compounds are isomers of
A) Oxidation B) Addition C) Polymerization
each other?
D) Esterification E) Saponification
I. Methyl acetate – methyl propanoate
II. Phenylacetic acid – methyl propanoate
III. Benzoic acid – phenyl formate

A) I only B) III only C) I and II 13. Which of the following pair of compounds are formed
by the reaction of methyl oleate with NaOH?
D) II and III E) I, II and III
A) Methyl alcohol and sodiumoleate
B) Methyl alcohol and oleic acid
C) Oleic alcohol and methanoic acid
D) Oleic acid and methanoic acid
10. For esters;
E) Oleic alcohol and sodium methylate
I. Hydrogen bonds exist between their molecules.
II. They are more soluble in water than in alcohols.
III. Liquids esters are good organic solvents.
Which of the above statements is(are) correct? 14. Which one of the following species is able to break up
the structure of the acyl group in an ester?
A) I only B) III only C) I and II

D) I and III E) I, II and III A) H2O B) KOH C) H2 D) NH3 E) NaOH

Esters 173
 WORD SEARCH
Try to find hidden words by the help of clues below.

CLUES
The reaction between carboxylic acids and alcohols pro-
duces these compounds (E) (6)
M Q E F S P R O S K S M R H X
R E H E A O S L V G Q A E H Q The common name of this compound is methyl ester (M)
O L T W D R A M H Q D I T C R (16)
F U W H E I E P O P E A A T A
F J T T Y H R Y T D P H W U S These compounds are triesters of fatty acids and glycerine
P Z S Z C L A E L W Y T D N M (F) (4)
E E M S I O F U C D A D R S I The ester derived from formic acid that has one H atom
L K F P G H W O R Y X R A A C bonded to C the atom of the functional group (M) (13)
K Q R T R P V O R J L R H T A
F A T S P M P Q V M B G C U X When esters are heated with aqueous solutions of strong
X D M D J H P R V P A F D R C bases such as NaOH and KOH, the salt of the carboxylic
H T V B O F S B K J X T V A I acid is produced which is known as a ____________ (S) (4)
G P Z B P N R I C T G D E T G Fats may be solid, liquid or molten depending upon the
N I I S E N I R A G R A M E W amount of ____________ they contain. (G) (9)
E C T Z A O I L L F V R S D S
If an oil is ____________ , this is because of the double
bonds in the fatty acids of this oil. (U) (11)

Because their melting points are higher than human body

temperature , they cause coronary diseases. These are not
preferred oils for human health. (M) (10)

Water containing Ca2+ and Mg2+ ions is known as

____________ (H) (9)

This is used to describe molecules or molecular groups that

mix poorly with water. (H) (11)

174 Oxygen And Nitrogen Containing Organic Compounds


Photosynthesis occurs in the leaves of
green plants. Plants take in CO2 in sun-
light (during the daytime) and give out
O2; humans and animals use O2 and
produce CO2. The oxygen abundance in
the air is 21% by volume which is the
most suitable percentage for the survival
of living organisms. The CO2 and O2
balance is kept constant by the produc-
tion of CO2 by animals and humans and
of O2 by plants. If the abundance of oxy-
gen in the air were 50%, everything
flammable would burn up instanta-
neously and it were 10 %, it would be
very difficult can be for humans and ani-
mals to survive. Thus, life would not exist
as we know it.
176 Oxygen And Nitrogen Containing Organic Compounds
INTRODUCTION
Carbohydrates are the most common compounds we encounter in daily life. The
doors we use in our houses, furniture in the form of wood, most of our food,
clothes made from cotton and linen are carbohydrates.
Carbohydrates are the most abundant organic compounds in nature, although
they are scarce in living organisms. Carbohydrates are the main energy and nutri-
tion source for all living organisms including human beings. Some of the more
common carbohydrates in our daily life are; cellulose which exists in plant tissue
and is a raw material for paper, starch which is an energy resource for plants,
glycogen which is used as an energy resource in animals and humans, glucose
and fructose which exist in fruit and honey, lactose, maltose and sucrose.
Carbohydrates are mostly produced by green plants. In the leaf of a green plant
carbon dioxide from the air and water, taken in from the roots of the plant, are
converted into glucose by the catalysts chlorophyll and sunlight. This process is
known as photosynthesis.
Plants, in fact, can be viewed as a natural laboratory that synthesizes organic
nutrition materials. Formaldehyde is produced in photosynthesis as a primary
product. However, as formaldehyde is a poisonous compound, plants polymer-
ize it into starch, cellulose and other complex compounds thereby transforming
it into useful, non-toxic substances. The general equation of photosynthesis is
sunlight
6CO2(g) + 6H2O(l) o C6H12O6(s)+ 6O2(g)
chlorophyll
As can be seen from the reaction, plants take carbon dioxide from the air and
convert it into oxygen. Living organisms can then use this oxygen to break down
carbohydrates to produce energy in the process of respiration.
C6H12O6(s) + 6O2(g) o 6CO2(g) + 6H2O(l) + Energy
The carbon dioxide produced can then used again by plants to produce more car-
bohydrates.
Photosynthesis and respiration in living organisms are the reverse of each other
and so the balance between the carbon dioxide and oxygen in the atmosphere is
controlled by these two processes.
1. STRUCTURE OF CARBOHYDRATES
The empirical formula of the most of carbohydrates is CH2O and the general for-
mula is Cn(H2O)m. Here, n=m or nzm. For this reason, carbohydrates may be
thought of as hydrated carbons (hence the name), though they do not contain
actual water molecules. The ratio of hydrogen atoms to oxygen atoms in a car-
bohydrate molecule is 2:1, as it is in water.
The simplest compound with the general formula of a carbohydrate is formalde- The general formula of carbohydrates is
hyde which has the formula CH2O. Hence, carbohydrates may be considered as Cn(H2O)m. But, a compound that has a
polymers of formaldehyde. formula of Cn(H2O)m is not necessarily a
O carbohydrate. For example, acetic acid
Ca(OH)2 has the formula C2(H2O)2 but is not a
6 H C H C6H12O6
formaldehyde glucose carbohydrate.

Carbohydrates contain the functional groups;

O O

alcohol (–OH), aldehyde ( C H ) and/or ketone ( C ).

Hence carbohydrates may be defined as polyalcohols of aldehydes and ketones. In

large carbohydrate molecules, ketone and aldehyde groups are not directly seen,
but when they are hydrolyzed, the aldehyde or ketone groups become apparent.

2. NOMENCLATURE OF CARBOHYDRATES
If a carbohydrate contains of an aldehyde group, it is named as an aldose; if it
contains a keto group, it is called a ketose. The number of carbon atoms deter-
mines the name of the carbohydrate.

H O H O H O H O
C C C C

H C OH H C* OH H C* OH H C* OH

H H C OH H C* OH H C* OH
glycolaldehyde
H H C OH H C* OH
aldotriose
(D–glyceraldehyde) H H C OH
aldotetrose
(D–erythrose) H
aldopentose
(D–ribose)

Aldoses

H C H2OH CH2OH

H C OH C O C O

H C O H C* OH H C* OH

H C OH CH2OH H C* OH
ketotetrose
H (D – erythrulose) CH2OH
ketotriose ketopentose
(dioxyacetone)

Ketoses

Carbohydrates 177
 C* indicates an asymmetric carbon atom, if the number of asymmetric carbon
atoms equals n, the optical isomers of the compound is calculated as 2n.

1
Name the following carbohydrates.
a. CHO b. CH2OH c. CHO d. CH2OH e. CH2OH

H C OH C O H C OH C O C O

H C OH H C OH HO C H H C OH H C OH

H C OH H C OH HO C H H C OH CH2OH

CH2OH CH2OH H C OH H C OH
CH2OH CH2OH

a. aldopentose b. ketopentose c. aldohexose

d. ketohexose e. ketotetrose

3. CLASSIFICATION OF CARBOHYDRATES
Carbohydrates can be classified as monosaccharides, disaccharides and poly-
saccharides according to the number of their carbon atoms.

3.1. MONOSACCHARIDES

Monosaccharides, commonly found in
foods, are hexoses. Most monosaccharides
can be fermented.
Fermentation of Glucose
1. Preparation of ethyl alcohol.
yeast
C6H12O6 o2C2H5OH + 2CO2n
2. Formation of lactic acid.
yeast
C6H12O6 o2CH3 –– CH–– COOH
l
OH
3. Fatty acid.
C6H12O6 oC3 H7 COOH + 2CO2n + 2H2n
General Properties
1. The number of carbon atoms in the structure of a monosaccharide is
between two and nine. Monosaccharides cannot be hydrolyzed to obtain
smaller carbohydrate molecules.
Glucose is a well-known monosaccharide. It is vitally important for the pro-
duction of energy in the metabolic processes of living organisms.
It is stored in the liver and muscles. It is present in grapes and honey.
2. Monosaccharides are white, crystalline, sweet compounds. They are very sol-
uble in water due to hydrogen bonding. They are only slightly soluble in alco-
hol and insoluble in nonpolar solvents such as ether and hydrocarbons.
3. The most important monosaccharides are glucose, fructose, mannose and
galactose. Their molecular formulae are identical (C6H12O6) and as such
they are all structural isomers of each other.

178 Oxygen And Nitrogen Containing Organic Compounds

 H C O CH2OH H C O CH2OH
* *
H C OH C O HO C H C O
* * * *
HO C H HO C H HO C H HO C H
* * * *
H C OH H C OH H C OH HO C H
* * * *
H C OH H C OH H C OH H C OH

CH2OH CH2OH CH2OH CH2OH

D–glucose D–fructose mannose D–galactose
(aldohexose) (ketohexose) (aldohexose) (ketohexose) Glucose, one of the most important
member of monosaccharides, is found
4. Because of their structural formulae, monosaccharides have four asymmet- in grapes.
rical carbon atoms in their solid state. Consequently, they show optical activ-
ity. For example, glucose, which is known as an aldohexose, contains four
asymmetrical carbon atoms, so it has
n
2 = 24 = 16 optical isomers.

Fructose, known as fruit sugar as

fruits contain large amounts of it ,
is sweeter than saccharose. It is
found mostly in honey (1/3 of
honey is fructose).

Cyclic Structures of Monosaccharides

Monosaccharides can have both cyclic and straight chain structures.
Cyclomonosaccharides are formed when straight-chain monosaccharides are
dissolved in water. In this case, the number of asymmetrical carbon atoms
increases to five. This process is known as hemiacetal formation . Let us exam-
ine the formation of the cyclic structure in the glucose molecule.
O OH
1
H C H C*
2
H C* OH H C* OH
3
OH C* H OH C* H O
4
H C* OH H C* OH
5
H C* OH H C*
6
CH2OH CH2OH Honey is an important source of mono-
saccharides.

Carbohydrates 179
 CH2OH

5C OH

H
CH2OH CH2OH
H H 5 O 5 O
H H H H H OH
4C OH H C O Þ 4
OH H
1 or 4
OH H
1
1 HO OH HO H
HO C C 3 2 3 2
3 2
H OH H OH
H OH
a) D–glucose b) a–D–glucose c) b–D–glucose
(a–D–glucopyranose) (b–D–glucopyranose)

a. The dissolving of D–glucose in water to form a cyclic structure.

b. D–D–glucose; –OH groups on 1st and 4th carbons are in the cis position.
c. E–D–glucose; –OH groups on 1st and 4th carbons are in the trans position.

2
Show the cyclic form of fructose when it is dissolved in water.

As we know, fructose is a ketohexose (the carbonyl group is on the second car-

bon). When it is dissolved in water an oxygen bridge is formed between its 2nd
and 5th carbon atoms.
CH2OH

C O
O
OH C H HO CH2OH

H C OH OH H
HOCH2 H
H C OH H OH
CH2OH

Oxidation of Monosaccharides
To determine the structure of carbohydrates the following oxidizing agents are
used.

1. Oxidation by Tollens’ and Fehling’s Reagents

a. Aldoses reduce Tollens’ reagent because of the aldehyde group in their struc-
ture. They also reduce Fehling’s solution in the presence of copper ions in
basic solution. The deep blue color of the solution is turned the red due to
cuprous oxide precipitation.

180 Oxygen And Nitrogen Containing Organic Compounds

 O O

H C C OH

H C OH H C OH

HO C H HO C H
+ 2Cu+2 + 4OH– + Cu2O(s) + 2H2O
H C OH Fehling’s reagent H C OH red precipitate

H C OH H C OH

CH2OH CH2OH
D – glucose gluconic acid

This reducing property is used to measure blood sugar in terms of glucose

units. If a sample of urea is mixed with Fehling’s reagent, a red precipitate is
observed.

b. Ketoses also reduce both Fehling’s and Tollens’ reagents. For example, fruc- All monosaccharides and disaccharides
tose, a ketohexose, does not show reducing properties in the solid state, but (except saccharose) are reducing sugars.
However, polysaccharides are not reduc-
in solution it reacts with Tollens’ and Fehling’s reagents as follows. ing sugars.
O
CH2OH
First this keto group C OH
is converted into an aldehyde
C O group, then it is oxidized
to a carboxylic acid. H C OH
HO C H
HO C H
+ 2Ag++2OH– + 2Ag(s)+H2O
H C OH Tollens’ reagent silver mirror
H C OH
H C OH
H C OH
CH2OH
CH2OH
D–fructose
(Ketohexose) gluconic acid

O
CH2OH
C OH
C O
H C OH
HO C H
HO C H
H C OH + 2Cu+2+4OH– + Cu2O(s) + 2H2O
Fehling’s reagent H C OH red precipitate
H C OH
H C OH
CH2OH
CH2OH
D – fructose
(Ketohexose) gluconic acid

Carbohydrates 181
 2. Oxidation of Monosaccharides with Bromine Water

Bromine water is an oxidizing agent that oxidizes the aldehyde group to the car-
boxyl group and aldoses to aldonic acids.
O O

C H Br2(aq) C OH
H2O
(CHOH)n (CHOH)n

CH2OH CH2OH
aldose aldonic acid

3. Oxidation of Monosaccharides with Nitric Acid

Nitric acid, a stronger oxidizing agent than bromine water, oxidizes both the alde-
hyde and the –CH2OH group to the carboxyl group and aldaric acid is formed.
O O

C H HNO3 C OH
H2O
(CHOH)n (CHOH)n

CH2OH C OH

O
aldose aldaric acid

3
36 grams of an aldose with the general formula of CnH2nOn is reacted with Tollens’
reagent and 43.2 grams of silver is precipitated. What is the molecular formula of
the aldose? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol, Ag : 108 g/mol)

Aldose with Tollens’ reagent;

CnH2nOn + 2Ag(NH3)2+ + 2OH– o CnH2nOn+1 + 2Agp + 4NH3 + H2O

Molar mass of aldose CnH2nOn = 12n + 2n . 1 + 16n = 30n g/mol

30n grams of aldose precipitates 216 g Ag

36 grams of aldose precipitates 43.2 g Ag
————————————————————————————
36 . 216
n = —————— = 6
30 . 43.2
Molecular formula is C6H12O6.

182 Oxygen And Nitrogen Containing Organic Compounds

 Detection of Sugar in Urine
Most sugars contain aldehyde or ketone groups in their structure. Hence, sug-
ars can reduce metallic ions such as Cu2+, Hg2+, Bi3+ and Ag1+ as they are oxi-
dized to carboxylic acids. This property can be used to detect the amount of
sugar in blood from urine samples .Although there are many different methods
to detect sugar in urine, the most important one is using Fehling’s solution
(reagent).

The procedure of this experiment is as follows:

1. In a test tube, add some Fehling I solution (7% CuSO4 solution).

2. Next, add an equal volume of Fehling II solution (a solution of sodium

potassium tartrate and NaOH) and make up to 100 ml with water.

3. Mix the solution well to produce a dark blue color.

4. Next, boil the solution (Attention: the dark blue color should not disappear,
if the color disappears, the indicator or test tube is not clean).

5. Finally the urine is added to the solution. (The amount of urine should not
exceed the amount of the indicator).

If the urine contains glucose (sugar) a yellow or red precipitate forms in the test
tube.

O O

C H C OH
+2 –
+ 2Cu +4OH ( C H OH)4 + Cu2O(s) + 2H2O
( C H OH)4 Fehling’s reagent red
precipitate
CH2OH CH2OH
gluconic acid
D–glucose

The amount of glucose in blood should be around 80-120 mg. Glucose disorder
in blood is related to the production of the hormone insulin.

4
500 g of a sample is taken from a glucose solution 1.2% by mass. If this sample
is reacted with excess Fehling’s solution, how many grams of Cu2O will be pre-
cipitated?
(C6H12O6 : 180 g/mol, Cu2O : 143 g/mol)

Carbohydrates 183
 Let us find the total amount of glucose
1.2
mglucose = 500 . ——— = 6 g.
100
The reaction of glucose with Fehling’s solution:
O O

C H C OH

(CHOH)4 + 2Cu+2 + 4OH– (CHOH)4 + Cu2O¯ + 2H2O

CH2OH CH2OH

According to the reaction;

180 grams of glucose precipitates 143 grams of Cu2O
6 grams of glucose precipitates x grams of Cu2O
————————————————————————————————
6 . 143
x = ————— = 4.77
180

x = 4.77 grams of Cu2O precipitates

Reduction of Monosaccharides
Aldehyde and ketone groups in monosaccharides can be reduced by strong
reducing agents. For example D–glucose can be reduced to D–glucitol (sorbitol)
by NaBH4 or H2 in the presence of Pt.

O H

H C H C OH

H C OH H C OH

HO C H +NaBH4 HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH
D – glucose D – glucitol
(sorbitol)

184 Oxygen And Nitrogen Containing Organic Compounds

 5
Write the reactions of D-ribose (an aldopentose) with;
a. Tollens’ reagent b. NaBH4

a. O O

C H C OH

(CHOH)3 + 2Ag+ + 2OH– (CHOH)3 + 2Ag¯ + H2O

Tollens’ reagent
CH2OH CH2OH
D–ribose

b. O H

C H H C OH
+NaBH4
(CHOH)3 (CHOH)3

CH2OH CH2OH
D–ribose

6
Write the reactions of D-ribulose (a ketopentose) with;
a. Tollens’ reagent b. NaBH4

a. CH2OH O

C O C OH

(CHOH)2 + 2Ag+ + 2OH– (CHOH)3 + 2Ag¯ + H2O

Tollens’ reagent
CH2OH CH2OH
D–ribulose

b. CH2OH CH2OH

C O +NaBH4
H C OH

(CHOH)2 (CHOH)2

CH2OH CH2OH
D–ribulose

Carbohydrates 185
 3.2. DISACCHARIDES
Condensation compounds derived by the elimination of a water molecule
from two monosaccharide molecules are called disaccharides. The two mono-
saccharides are linked via an oxygen bridge.

The aldol condensation is the reaction of General Properties

two identical aldehydes or ketones in
1. Their general formula is C12H22O11 .
the presence of a base such as sodium
carbonate, barium hydroxide or dilute 2. They are white, crystalline and sweet compounds.
sodium hydroxide.
3. All of them rotate plane–polarized light to the right.

4. They hydrolyse to form monosaccharides.

5. In nature, the most important disaccharides are sucrose (table sugar, cane
sugar or beet sugar) maltose (barley sugar), lactose (milk sugar) and cel-
lobiose.

Saccharose (Sucrose)
Saccharose is formed by linking of one molecule of glucose to a fructose mole-
cule. It occurs widely in plants and is particularly abundant in sugar cane and
sugar beet from which it is extracted and refined for use as table sugar. It dis-
solves well in water and is slightly soluble in alcohol. When sucrose is digested,
If sucrose is heated above its melting glucose and fructose are formed which are then absorbed into the blood.
point it turns into caramel which is used –H2O
in the production of candies. C6H12O6 + C6H12O6 o C12H22O11 + H2O
glucose fructose sucrose
(table sugar)

Or in more detail,

O
O H CH2OH CH2OH

H C HO C H C C

H C OH HO C H H C OH HO C H
+ O O + H2O
HO C H O H C HO HO C H O H C OH

H C OH H C H C OH H C

H C CH2OH H C CH2OH

CH2OH D–fructose CH2OH

D–glucose
saccharose (sucrose)

186 Oxygen And Nitrogen Containing Organic Compounds

 CH2OH CH2OH
O O
O H HOCH2 O H HOCH2
H H H H H H
C + C C C + H2O
OH OH H H HO CH2OH OH OH H H HO CH2OH
OH OH O
H OH OH H H OH oxygen OH H
glucose fructose bridge
saccharose (sucrose)

Cyclic structure of sucrose.

Saccharose (sucrose) does not show reducing properties as it does not contain
a carbonyl group (aldehyde, D-hydroxy ketone or hemiacetal group). Hence it
does not react with Tollens’ and Fehling’s reagents.

Lactose
Lactose is known as milk sugar and occurs in the milk of all mammals. Human
milk contains 6%, and cow’s milk 4% lactose.
C6H12O6 + C6H12O6 o C12H22O11 + H2O
glucose galactose lactose

The structure of lactose is given below.

CH2OH
O
H OH
C
id en

CH2OH OH H H
br xyg
ge
o

O O H
OH H H OH
C glucose
H OH H
H
H OH
galactose Lactose is the substance which gives a
sweet taste to human and animal milk.
Upon reaction with dilute acids, it is hydrolyzed to glucose and galactose. Glucose and galactose may be convert-
ed into lactic and butyric acids by the
Maltose effect of some yeasts, this causes milk
Maltose is a disaccharide that is present free in small quantities in barley grains to turn sour.
and other plants. However, it is more commonly produced by the action of the
amylase enzyme on starch or glycogen. Its melting point is 102-103 °C.
It is used in the production of soft drinks and foods.
Maltose, because of the free aldehyde group in its structure, reduces Fehling’s
solution and produces a monocarboxylic acid (maltonic acid) with bromine
water. When hydrolyzed by dilute acids maltose forms two glucose molecules.

Carbohydrates 187
 It is the only dissaccharide that rotates plane–polarized light to the left.
H2O
C12H22O11 o C6H12O6 + C6H12O6
maltose glucose glucose

CH2OH CH2OH
O H H O
H H H H

OH OH H OH H OH
O
H OH H OH
glucose glucose
maltose

Cellobiose
Cellobiose is produced by the partial hydrolysis of cellulose (a polysaccharide) .
If the hydrolysis continues, two molecules of glucose are produced. Cellobiose is
very similar to maltose, they are geometrical isomers. In some countries, cel-
lobiose is produced by heating wood with hot acids and used as fodder for ani-
mals.
+H2O
C12H22O11 o
+
C6H12O6 + C6H12O6
H
cellobiose glucose glucose

3.3. POLYSACCHARIDES
Polysaccharides are polymers of monosaccharides. Polysaccharides are formed
by linking many monosaccharides together with an oxygen bridge.

General Properties
1. Their general formula is (C6H10O5)n .
2. They occur in the roots, tubers and seeds of plants.
3. They are noncrystalline, amorphous and tasteless substances; these are the
most significant properties differentiating polysaccharides from monosac-
charides.
4. They are the only carbohydrates that are insoluble in water, they form a col-
loidal structure when mixed with water. They are also insoluble in alcohols.
5. They can be broken down into monosaccharides when hydrolyzed.
6. The most important polysaccharides in nature are;
a. Starch,
b. Glycogen,
c. Dextrin,
d. Cellulose.

188 Oxygen And Nitrogen Containing Organic Compounds

Starch
Starch is the most important polysaccharide and is formed by combining glu-
cose molecules with a glycosidic linkage. Corn, potatoes, rice and the roots of
plants and seeds are the main sources of starch. Starch is an essential nutrition-
al resource.
One molecule of starch consists of thousands of glucose molecules.

CH2OH CH2OH
H O H H O H
H H Starch is an essential food for humans.
Bread is composed of 50–75% starch.
OH H OH H
O O O
H OH H OH
n
glucose glucose

Representation of the starch molecule.

Starch is insoluble in water. When it is heated with water, it is broken down into
simpler carbohydrates and forms a colloidal mixture.
Starch does not reduce Fehling’s reagent, though undergoes a characteristic
reaction with iodine, forming a deep blue solution.
Since it contains many –OH groups in its structure, starch absorbs moisture well.
When starch is heated with a dilute acid, it undergoes a hydrolysis reaction
resulting in glucose as the final product.
H2O H2O +H2O
(C6H10O5)n o
+
(C6H10O5)n o
+
C12H22O11 o
+
2C6H12O6
H H H
starch dextrin maltose glucose

Glycogen
Glycogen, stored in the livers and cells of animals, is the main carbohydrate Potato is one of the main source of
resource for animals. The molecule is built up of a large number of monosac- starch.
charide units by glucoside links. It is insoluble in water and gives a pink color
upon reaction with iodine. It is broken down in the digestive system to give glu-
cose and maltose.

Dextrin
Dextrins are produced by heating up starch to 160 – 228°C. Hence dextrins are
found in the crusts of bread. They dissolve in water but form a precipitate in alco-
hols.
They can also be obtained from the hydrolysis of starch with dilute acid at low
temperature. Dextrins are mixtures of polysaccharides having 5–15 glucose units
in their structure. They are sticky, sweet substances used in the manufacture of
adhesives and soft drinks.

Carbohydrates 189
 Cellulose
Cellulose is the most abundant organic substance in nature. The walls of plant
cells are made of cellulose. The main cellulose sources in nature are wood,
grass, hay, cotton, linen and hemp.
Cellulose molecules may be formed from more than 3500 glucose units. Cellulose
is an amorphous substance, insoluble in water and unlike other polysaccharides,
resistant to dilute acids and bases. However, it can be hydrolyzed by dilute acids
under high pressures and temperatures.

+H2O +H2O
Cellulose o
+
Cellobiose o
+
Glucose
H H

CH2OH
H O O
H

OH H
O H
H OH
n
glucose

Structure of cellulose

Cellulose is an important raw material for many different commercial substances:

1. Trinitrocellulose ([C6H7O2(ONO2)3]n) is known as cotton gunpowder and is

used to produce smokeless explosives . It is also used in the production of
films and artificial leather.

H2SO4
[C6H7O2(OH)3]n + 3nHNO3 o [C6H7O2(ONO2)3]n + 3nH2O
cellulose trinitrate
(cotton gunpowder)

2. Rayon is produced by dissolving cellulose in carbon disulfide in a basic medi-

Cellulose is the main component of
wood and its derivatives. 60-70% of
wood is cellulose.
um. This reaction yields cellulose xanthate. The solution of cellulose xanthate
is then passed through a small slit into an acidic solution.
This reaction leads to precipitation in the form of a fiber. It is this fiber that
is rayon.

3. After treating cellulose with sulfuric acid and acetic acid, cellulose triacetate
is produced. Cellulose triacetate and its derivatives are used in the textile
industry and in the production of films.

4. Cellulose fibers are the most important material in paper production.

190 Oxygen And Nitrogen Containing Organic Compounds

1. Which materials in your house contain carbohydrates? 12. Classify carbohydrates and give one example from each
Research. group.

2. What is the importance of carbohydrates for living

organisms?
13. What are the general properties of monosaccharides?

3. What are the most important carbohydrates around us?

14. What is the importance of glucose among the mono-

4. Explain photosynthesis. saccharides?

5. What is chlorophyll? What is its function?

15. What is the reason for the easy hydrolysis of glucose in
water?
6. What is the primary product of the photosynthesis
process?

16. What is mutarotation? Explain

7. Explain the relationship between respiration and photo-
synthesis. Why is the balance between these two
processes important for living organisms?

17. Explain how hemiacetals are formed.

8. Define carbohydrates and give their general formulae.

9. Describe the structures of carbohydrates.

18. What are the main oxidizing agents used to oxidize
monosaccharides to carbonic acids?

10. Which functional groups do carbohydrates contain?

Explain.

19. What do you understand from the terms D-hydroxy and

E-hydroxy?
11. Write the structural formulae of the carbohydrates given
below.
a. Ketopentose
b. Aldotetrose
c. Ketohexose 20. What are the functional groups that exist in monosac-
d. Aldohexose charides?

Carbohydrates 191
21. Why don’t ketoses of monosaccharides show reducing 29. What is the most important property that differentiates
properties when they are split? Explain. monosaccharides from disaccharides?

22. What is the molecular formula of the aldose of which 36 30. Which monosaccharides are produced by the hydrolysis
grams reacts with Fehling’s solution to produce 28,6 of sucrose (saccharose)?
grams of Cu2O?

31. What are the reasons for saccharose showing reducing

23. How many grams of Cu2O are formed when 30 grams
properties?
of 60% glucose solution react with excess Fehling’s solu-
tion? (Cu: 63.5 g/mol)

32. What is invert sugar? Explain.

24. How many grams of silver are produced when 45 grams

of 80% glucose solution react with ammoniacal silver
nitrate solution (Tollens’ reagent)?
33. What are the general properties of polysaccharides?

25. When 20 grams of glucose solution react with ammoni-

acal copper(I) chloride solution (Fehling’s reagent) 14.3 34. What is the most important property of polysaccharides
grams of Cu2O are precipitated. What is the mass per- that differentiates them from other carbohydrates?

centage of this solution?

35. What are the most important polysaccharides in nature?

26. 45 grams of an aldose having the general formula
CnH2nOn produces 35.75 grams of Cu2O when reacted
with excess Fehling’s solution. According to this;
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol) 36. What is the importance of starch for living organisms?
Which plants contain starch?
a. What is its molecular formula?
b. What is its molar mass?

37. What are the main sources of dextrin, glycogen and cel-
lulose?
27. What are the general properties of disaccharides?

28. What are the most important disaccharides in nature? 38. In which areas is cellulose used?

192 Oxygen And Nitrogen Containing Organic Compounds

1. Which one of the following is the main source of carbo- 5. H CH2 OH
hydrates?
C O C O
A) Stones B) Sedimentary rock H C OH CH2 OH
C) Green plants D) Soil CH2 OH
E) Air X Y

Which of the following is(are) correct for the compounds

above? They are;
I. optically active
2. Which one of the following is incorrect for photosynthe- II. isomers of each other
sis?
III. carbohydrates
A) It occurs in the porous leaves of green plants.
A) I only B) II only C) III only
B) Sunlight is used as an energy source.
D) II and III E) I and II
C) It turns CO2 from the air into carbohydrates.
D) Respiration in animals and humans is the same as
photosynthesis.
E) It occurs using the catalyst chlorophyll.

3. Fill in the blank given below with suitable word.

Carbohydrates are ............... that contain aldehyde or
ketone groups in their structures.

A) Ethers B) Esters C) Aldehydes

D) Polyesters E) Polyalcohols

6. Which one of the following is incorrect for carbohydrates?

4. I. H II. H III. H
A) Monosaccharides are the simplest sugars.
C O C O H C OH
B) Monosaccharides are straight chained molecules.
H C OH H C OH C O
C) Disaccharides are formed by the combination of two
CH3 H2C OH H 2C OH monosaccharide molecules.

Which of the molecules above is (are) carbohydrates? D) If three or more monosaccharide molecules com-
bine they form polysaccharides.
A) I only B) II only C) III only E) Monosaccharides cannot be hydrolyzed to simpler
D) II and III E) I and II molecules.

Carbohydrates 193
7. Which one of the following is incorrect for monosaccha- 10. The fermentation reaction of glucose is;
rides? yeast
C6H12O6 o 2C2H5OH + 2CO2
A) They cannot be hydrolyzed to simpler molecules. How many grams of ethyl alcohol is produced from 90
B) They can enter the blood stream directly. grams of a 60% of glucose solution?
C) Monosaccharides are the only class of carbohydrates A) 13.8 B) 18.4 C) 23 D) 27.6 E) 32.2
that can be fermented.
D) The most important are glucose, fructose, mannose
and galactose.
E) They do not show optical activity.

11. Which statement is incorrect for disaccharides?

A) Their general formula is C12H22O11 .

B) They are all soluble in water.
8. Which one of the following is wrong for glucose?
C) They are the condensation product of at least two
A) It is the most common sugar in nature and is known monosaccharides.
as blood sugar. D) The most important are saccharose, maltose, lac-
tose and cellobiose.
B) It can be fermented by yeast.
E) They are more soluble in alcohol than in water.
C) It can be oxidized to a carboxylic acid by Fehling’s
reagent.
D) It can be reduced to a polyalcohol by NaBH4 .
E) Mutarotation is not a property of aqueous solutions
of glucose.

12. Which statement is correct for sucrose?

A) It is widely found in grapes and honey.

B) It is formed by combination of two molecules of glu-
cose.
9. How many grams of 20% glucose solution should be
C) It is slightly soluble in water and highly soluble in
used to produce 28.6 g of Cu2O from Fehling’s solution?
alcohol.
(C6H12O6 : 180 g/mol, Cu2O : 143 g/mol)
D) It doesn’t show any optical activity.
A) 180 B) 360 C) 90 D) 45 E) 286 E) It doesn’t react with Fehling’s and Tollens’ reagents.

194 Oxygen And Nitrogen Containing Organic Compounds

13. Which one of the following statements is incorrect?
A) Lactose is known as milk sugar and is not found in
plants.
B) Maltose is formed by the combination of two mole-
cules of glucose.
C) Lactose is formed by linking glucose and mannose
molecules together by glucoside bonds.
D) Maltose and cellobiose are geometrical isomers of
each other.
E) Cellobiose shows exhibits properties.
14. What is the mass percentage of a saccharose solution if
228 grams of it produces 72 grams of glucose after
hydrolysis in acidic medium?
(C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)
A) 60 B) 50 C) 40 D) 30 E) 20
15. Which one of the following is incorrect for polysaccha-
rides?
A) They are highly soluble in water.
B) They don’t have a stable crystalline structure.
C) When they are hydrolyzed, they can be broken down
into monosaccharides.
D) They are found in plant and animal tissues.
E) The most common polysaccharides are starch, cel-
lulose and glycogen.
16. Which one of the following statements describing poly-
saccharides is incorrect?
A) They don’t have a definite melting point, they sub-
lime.
B) Starch reacts with Fehling’s reagent.
C) The hydrolysis of starch by dilute acid produces dex-
trin.
D) Cellulose is the most common organic substance
and forms the walls of plant cells.
E) Their general formula is (C6H10O5)n .
Carbohydrates 195
 CRISS – CROSS PUZZLE
Solve the clues and place your answers in their correct positions in the grid.

1 2 3

5 6

7 8

10

CLUES ACROSS CLUES DOWN

4. It is the process by which carbon dioxide from air and
water from the roots of plants are converted into glu-
cose under the catalysts of chlorophyll and sunlight.
5. Glucose molecules can be combined to form large
molecules of __________, which serves as a reserve
material. It is an essential source of nutrition. Corn,
potatoes, rice and seeds are the main sources of this
substance.
6. It is the most important monosaccharide, it is the most
abundant sugar found in nature and in animals.
1. A class of carbohydrate that contains many monosac-
charide units, examples are starch and cellulose.
2. The chief constituent of the cell wall of all plants and the
most abundant organic substance found in nature. It is
the main component of wood.
3. If a carbohydrate contains a keto group it is named as
a ______________
8. If a carbohydrate contains an aldehyde group it is
named as an _______________

7. It is known as fruit sugar because large amounts of this

sugar exist in fruits.

9. A hydroxy aldehyde, a hydroxy ketone or a substance

derived from these compounds.

10. A carbohydrate molecule that is composed of two

monosaccharide units

196 Oxygen And Nitrogen Containing Organic Compounds

 INTRODUCTION
Amines, amides, amino acids and proteins, can be straight chained or branched
molecules.
Amines are derivatives of ammonia having general formula R NH2 .
Amides have the general formula R CO NH2 .
Amino acids are compounds having both an amine ( NH2) and a carboxyl
group ( COOH) in their structure.
Proteins are long chained amino acid molecules.

1. AMINES
Amines are weak bases that can be described as organic derivatives of ammonia
or as alkylated ammonia compounds.

The functional group of amines is the amino group ( NH2). The nitrogen atom
undergoes sp3 hybridization and is attached to one or more carbon atoms.
Amines can be classified as primary, secondary or tertiary amines depending
upon the number of alkyl groups attached to the nitrogen atom.
Heterocyclic Amines
H N H R N H R N H R N R¢¢
In these compounds N is a part of a
ring structure. H H R¢ R¢
ammonia primary amine secondary amine tertiary amine

R can be an alkyl or an aryl group.

N N N

H H H3C N H H3C N C2H5 H N N

pyrrolidine pyridine pyrrole
H H H H
methylamine ethylmethylamine phenylamine diphenylamine

1.1. NOMENCLATURE OF AMINES

Common Names
1. Primary amines are commonly called alkylamines, though systematically,
they are named alkaneamines.

CH3

CH3 NH2 C2H5 NH2 CH3CH2CH2 NH2 CH3 CH NH2

methylamine ethylamine propylamine isopropylamine
(methane amine) (ethane amine) (propane amine) (isopropane amine)

198 Oxygen And Nitrogen Containing Organic Compounds

 H CH3 NH2
NH2 CH3CH2 C NH2 CH3 C NH2
CH3 CH3 Some Amines
phenylamine sec–butylamine tert–butylamine b – naphtylamine
Amines occur widely in plants and ani-
(aniline)
mals. They can easily be extracted from
their sources by treatment with acids.
2. When naming the secondary and tertiary amines, the smaller group is writ- Amines are basic compounds, alterna-
ten first and the other groups are added before the word “–amine”. If the tively named as ALKALOIDS. Today,
groups are the same , the di- or tri- prefixes are used . In common nomen- there are 5000 alkaloid compounds
known to be biologically active.
clature we use the locant N to designate substituents attached to a nitrogen
atom. Cocaine and morphine are two very
well known alkaloids. Cocaine is a
compound extracted from the leaves of
CH3 the coca plant. Long term usage of
CH3 NH C2H5 C2H5 NH CH CH3 C3H7 NH C4H9 cocaine causes addiction and harms the
central nervous system.
ethylmethylamine ethylisopropylamine propylbutylamine
O OCH3 HO
N–ethyl–N–methylamine N–ethyl–N–isopropylamine N–propyl–N–butylamine C
O
N OCC6H5
H CH3
O
NCH3
H
N C2H5 NH C2H5 CH3 N CH3
HO
CH3 cocaine morphine

diphenylamine diethylamine trimethylamine Morphine, also known as ascocaine, is

N, N–diphenylamine N, N–diethylamine N, N, N–trimethylamine also an addictive substance. The diac-
etate salt of morphine, heroin, is as
C2H5 C2H5
addictive as morphine and cocaine.
N(CH3)2
CH3 N CH3 C2H5 N C3H7 Many different alkaloids, such as nico-
tine and quinine, contain more than
dimethylethylamine diethylpropylamine dimethylcyclopentylamine one nitrogen atom in their structure.
N, N–dimethyl–N N, N–diethyl–N N–N–dimethyl–N
–ethylamine –propylamine –cyclopentylamine Quinine is used in medicine to cure the
disease malaria. Nicotine is a color-
less, poisonous alkaloid present in
3. In the systematic naming (IUPAC) of these compounds, the –NH2 amine large amounts in tobacco. As it is
highly toxic, its salts are used as insec-
group is called the amino group. This naming is generally used in the case of
ticides.
alcohols and acids.
OH H2N OH H H
HO
3 2 1 5 4 3 2 1 N
H2N CH2CH2CH2 OH H2N CH2CH CH2CH CH2 CH3O
N

CH3
3 – amino – 1 – propanol 2,5 – diamino – 1,4 – propanediol N

O OH quinine nicotine

3 2 1 3 2 1
H2N CH3 H2N CH2CH2 C OH H2N CH2CH2CH NH2

p – aminotoluene 3 – aminopropanoic acid 1,3 – diamino – 1 – propanol

Amines, Amides And Amino Acids 199

 1
Name the following amine compounds.
a. CH3 b. C2H5 N C2H5
Have you ever heard?
CH3 N C2H5 C2H5
Chocolate contains phenylethylamine,
a chemical related to psychomotor CH3
stimulants and raises blood pressure
c. CH3 C NH2 d.
and blood glucose levels. The result is NH2
that we feel more alert and gives us a CH3
sense of well being.
e. f.
NH2 CH2CH2 NH2

a. dimethylethylamine b. triethylamine
c. tert-butylamine d. cyclopentylamine
e. phenylamine (aniline) f. 2 – phenylethylamine

Phenylethylamine is known as the

“love drug” and is thought to be the 2
reason why chocolate is said to be an
Write the structures for the given compounds.
aphrodisiac. It is a chemical that mim-
ics the brain chemistry of a person in a. Diethylmethylamine
love, so when levels of phenylethy- b. 2-aminopentane
lamine are high in the body it relieves c. 1,4-diamino - 1,4 - butanediol
depression from unrequited love. This d. Ethylmethylisopropylamine
is one of the reasons so many women
love chocolate - it really changes mood
of person.
5 4 3 2 1
a. C2H5 N C2H5 b. CH3 CH2 CH2 CH CH3

CH3 NH2

H H CH3
4 3 2 1
c. H2N C CH2 CH2 C NH2 d. C2H5 N CH CH3

OH OH CH3

3
What is the molecular formula of the tertiary amine which contains 65.75% C,
19.18%N and 15.07%H, by mass? (C : 12 g/mol, N : 14 g/mol, H : 1 g/mol)

200 Oxygen And Nitrogen Containing Organic Compounds

Let us assume we have 100 g of this amine. Then the mole ratio of the elements are
65.75 g 19.18 g
nC = ––––––––––– = 5.48 mol, nN = ––––––––––– = 1.37 mol
12 g/mol 14 g/mol

15.07
nH = ––––––––– = 15.07 mol
1 g/mol

If the mole numbers of the compounds are divided by smallest mole number, 1.37
mol, the following integers are found.
5.48 1.37 15.07
nC = ––––––– = 4 mol nN = –––––– = 1 mol nH = ––––––– = 11 mol
1.37 1.37 1.37

C4H11N is the formula. Since this is a tertiary amine the structural formula must be;

CH3 N CH3

C2H5

1.2. PHYSICAL PROPERTIES

Small amine molecules are generally gaseous and are soluble in water. Amines
have a very bad odor, similar to that of ammonia and tainted fish.
Amines, like ammonia, are polar compounds (though tertiary amines less so as
they have no N–H bond). Because of the N–H bonds in their structures, primary
and secondary amines form hydrogen bonds between their molecules.
The boiling points of amines are higher than those of the equivalent alkanes and
ethers but lower than the equivalent alcohols and carboxylic acids. Amines have a tainted fish smell.

C2H5 O C2H5 (C2H5)2NH CH3CH2CH2CH2OH

H CH3 H
diethyl ether diethyl amine 1 – butanol
– – +
d d d
bp : 54.6 °C bp : 55 °C bp : 118 °C CH3 N H N H N CH3
d+
Since tertiary amines do not contain N–H bonds, they can not form H H
hydrogen bonds in the liquid state and so their boiling points are lower
than those of primary and secondary amines. intermolecular H – bonding in amines

All low molecular weight amines are very soluble in water.

Because of the lone pair
CH3CH2CH2 NH2 CH3CH2 NH CH3 (CH3)3 N of electrons on the nitro- Hydrogen
bond H
propylamine methylethylamine trimethylamine gen atoms, all amines
bp : 40 °C bp : 37 °C bp : 3 °C form hydrogen bonds (CH3)3N : H O
with water.

Amines, Amides And Amino Acids 201

 Melting Boiling Solubility
Name Structure Point Point (g/100 mL Kb
(°C) (°C) water)
Methylamine CH3NH2 – 94 –6 very soluble 4.4 · 10–4
Ethylamine CH3CH2NH2 – 81 17 very soluble 4.7 · 10–4
Propylamine CH3CH2CH2NH2 – 83 49 very soluble 4.0 · 10–4
Dimethylamine (CH3)2NH – 92 7 slightly soluble 5.0 · 10–4
Trimethylamine (CH3)3N – 117 3 slightly soluble 6.0 · 10–5
Aniline C6H5NH2 – 6 184 soluble 4.2 · 10–10

Table 1: Physical properties of some amines.

1.3. CHEMICAL PROPERTIES AND REACTIONS

Amines are basic compounds. They form hydrogen bonds upon dissolving in
water because the nitrogen atom in the amine has a lone pair of electrons simi-
lar to ammonia.
This means that they can form salts with Lewis acids.

+
H H
R N + H+Cl– R N H Cl–
H H
amine alkylammonium chloride salt

The basic strength of amines is weaker than that of hydroxide and alkoxide ions
but stronger than that of water.
–
–
[R NH3+] · [OH ]
R NH2 + H2O
 [R NH3]+ + OH Kb = –––––––––––––––––––––
[R NH2]
The order of basic strength for amines is;

R3N > R2NH > RNH2 > NH3

As we have said, amines react with acids to produce salts.

+
C3H7 NH2 + H+Cl– C3H7 NH3Cl–
propylamine propylammonium chloride

Ammonium salts can be converted back into amines by heating with strong bases.
+ heat
R NH3Cl– + Na+OH– R NH2 + NaCl + H2O
+ heat
CH3 NH3Cl– + Na+OH– CH3 NH2 + NaCl + H2O

202 Oxygen And Nitrogen Containing Organic Compounds

 4
A 500 mL solution of ethylamine is prepared by dissolving 0.1 mol of ethylamine
in water. What is the pH of this solution? (Kb of ethylamine = 5 . 10–4) Do You Know?
Even though many alkaloids (amines)
are poisonous, some are used in medi-
Molarity of 0.1 mol ethylamine in 500 mL solution; cine as analgesics (pain relievers) or
anaesthetics, particularly morphine
0.1 mol
M = –––––––––– = 0.2 mol/L and codeine.
0.5 L Most alkaloids have a very bitter taste.
+ –
C2H5 NH2 + H OH
C2H5 NH3 + OH

Initial : 0.2 M –– ––
Change : –x +xM +xM
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Equilibrium : (0.2 – x)M (+x) M (+x) M
+ –
[C2H5 NH3 ] [OH ] x2
Kb = ––––––––––––––––––––––––– 5 · 10–4 = –––––––––
[C2H5 NH2] 0.2 – x
–
Then x = [OH ] = 1 · 10–2 M If [H+][OH–] = 1 · 10–14
+
[H ] is 1 · 10–12 M
+
pH = – log [H ] = – log 1 · 10–12 = 12

1.4. PREPARATION OF AMINES

Reactions of ammonia with alkyl halides yield ammonium salts. Treating these
ammonium salts with bases produces primary amines.
If primary amines react with alkyl halides, secondary amines are produced. If the
reactions are allowed to proceed, tertiary amines can be obtained.

+OH–
NH3 + R–X o RNH2 (primary amine)
–
+OH
RNH2 + R–X o R2NH (secondary amine)
–
+OH
R2NH + R–X o R3N (tertiary amine)
Almost all organic compounds containing nitrogen in their structure can be
reduced to amines.
Unsaturated nitrogen compounds (nitriles) can be reduced by the addition of
hydrogen to give primary amines.
Ni
R C N + 4[H]+ RCH2 NH2
heat
primary amine

Amines, Amides And Amino Acids 203

 5
Complete the following reactions.
Reduction of Amides a. CH3 Cl + NH3
heat

Amides can be reduced to primary,

secondary or tertiary amines by a heat
b. C3H7 Br + NH3
strong reducing reagent such as
LiAlH4. Ni catalyst
c. CH3 NO2 + 3H2
O LiAlH4,
ether O
R C NH R¢ H2O
RCH2NR¢
amide amine LiAlH4
d. CH3 C NHC2H5

Ni
e. N C(CH2)4C N + 4H2

a. heat
CH3 CI + NH3 CH3 NH2 + HCl

heat
b. C3H7Br + 2NH3 o C3H7NH2 + NH4Br

c. The –NO2 group is converted to –NH2

Ni
CH3 NO2 + 3H2 CH3 NH2 + 2H2O

d. If amides are reduced by strong reducing agents the C=O bond is reduced
to CH2.

O
LiAlH4
CH3 C NHC2H5 CH3CH2 NH C2H5 + H2O

e. S bonds in C N are broken and the group is reduced to CH2 NH2

heat
N C (CH2)4C N + 4H2 o H2N (CH2)6 NH2

2. AMIDES
Amides are organic compounds derived from ammonia by replacing a hydrogen
with an organic acid group. Hence amides may be defined as compounds con-
taining a C O group.

NH2

204 Oxygen And Nitrogen Containing Organic Compounds

Amides can be classified as primary, secondary or tertiary according to the num-
ber of alkyl groups attached to the –N atom.
R C O R C O R C O
NH2 HN R R N R
primary amide secondary amide tertiary amide

2.1. NOMENCLATURE OF AMIDES

1. The simplest structure of amides is that in which the nitrogen is bonded to
two hydrogen atoms. In order to name these, use the name of the carboxylic
acid from which the amide is derived but replace the –ic or –oic suffix with
–amide.
O O O O
R R
H C OH CH3 C OH C2H5 C OH C6H5 C OH C O C O
formic acid acetic acid propionic acid benzoic acid OH NH2
carboxylic amide
acid
O O O O
Amides are compounds in which the
H C NH2 CH3 C NH2 C2H5 C NH2 C6H5 C NH2 –NH2 group is attached to the carbon
formamide acetamide propionamide benzamide atom of an acid in place of the –OH
group.
2. When naming secondary and tertiary amides, the groups attached to the
(–NH2) group are indicated by the prefix N– , and these group names prefix
the name of the corresponding primary amide .

O O CH3 O O CH3

H C NH CH3 H C N CH3 CH3 C N CH3 CH3 C N CH3

H
N – methylformamide N,N – dimethylformamide N – methylacetamide N,N – dimethylacetamide

2.2. PROPERTIES OF AMIDES

Amides have hydrogen bonds between their molecules and so their boiling
points are relatively high. For example, formamide is a liquid with boiling point
190°C while all other amides are white-crystalline solids. Since they are polar,
they are water soluble. They do not react with acids and bases, though when
heated slowly with water they are hydrolyzed.

2.3. PREPARATION OF AMIDES

Amides can be prepared by the reaction of ammonia, primary amines or second-
ary amines with acid anhydrides, esters or acyl chloride.

Amines, Amides And Amino Acids 205

 Nucleophilic addition
O O
heat
NH3 + R C Cl R C NH2 + HCl
ammonia acyl chloride primary amide

O O
heat
NH3 + CH3 C Cl CH3 C NH2 + HCl
ammonia acyl chloride acetamide

a. Acylation of primary amines leads to secondary amides.

Nucleophilic addition
O O
R NH2 + R C Cl R C NH R + HCl
primary amine acyl chloride secondary amide

O O
–HCl
C2H5 NH2 + CH3 C Cl CH3 C NH C2H5
ethylamine acetyl chloride N – ethylacetamide

b. Acylation of secondary amines produces tertiary amides.

R¢ O O R¢
NH + R C Cl R C N + HCl
R¢¢ acyl chloride R¢¢
secondary tertiary
amine amide

O O CH3
CH3 N C3H7 + C2H5 C Cl C2H5 C N + HCl
C3H7
H
N – methylpropylamine N – methyl, N – propylpropionamide

Amides with an acyl group derived from acetic acid are called acetamides.
Acetamides are generally produced from the reactions of acetic anhydride with
amines.

O O

CH3 C O C CH3 + 2R NH2

acetic anhydride primary amine
O O
+ –
R NH C CH3 + R NH3 O C CH3
secondary amine alkylinium acetate

206 Oxygen And Nitrogen Containing Organic Compounds

2.4. UREA (CARBAMIDE)
Urea is colorless, water soluble and crystalline solid with a melting point of 132°C.
O

H2N C NH2
urea

Urea is obtained from the reaction between CO2 with NH3 at high temperature
and pressure. It can also be produced by the reaction of phosgene gas with
ammonia.
O
heat
CO2 + 2NH3 pressure H2N C NH2 + H2O
O O

Cl C Cl + 2NH3 H2N C NH2 + 2HCl

phosgene urea

It was first synthesized by Friedrich Wöhler in 1828 by evaporating a solution of

ammonium cyanate. Urea is found in small amounts in the blood of mammals.
Its principal industrial usage is in the manufacture of plastics (specifically,
urea–formaldehyde resin) and is also a component of many fertilisers, providing
a nitrogen source for plants.

3. AMINO ACIDS
Amino acids contain both amino (–NH2) and carboxyl (–COOH) groups in their
H
structure. Amino acids are the basic building blocks of proteins, which are the
basis of living organisms. There are over 700 naturally occurring amino acids. R C C O

The amino group in amino acids obtained from the proteins of plants and ani- NH2 OH
amino carboxyl
mals is in the D position with respect to the carboxyl group. group group

3.1. NOMENCLATURE OF AMINO ACIDS An amino acid molecule contains both

the amino and carboxyl group.
Amino acids are classified depending upon the relative positions of their func-
tional groups. The following examples show the idea.

H H H H H H H
a b a b a b a
H C COOH H C C COOH H C C COOH C C COOH

NH2 H NH2 NH2 H H NH2

a – aminoethanoic acid a – aminopropanoic acid b – aminopropanoic acid a – amino – b – phenylpropanoic acid
glycine a–alanine b–alanine phenyl alanine

Amines, Amides And Amino Acids 207

 3.2. PROPERTIES OF AMINO ACIDS
Because of the existence of both (the –NH2) and (the –COOH) groups, amino
acids display amphoteric properties (i.e., have both acidic and basic properties).

They form metal salts when reacted with basic solutions.

–
H H
+
R C COOH + NaOH R C COO Na + H2O

NH2 NH2

sodium salt of glycine

But amino acids behave as bases towards acidic solutions.

+
Fish is an important source of protein. H H
–
R C COOH + HCl R C COO Cl

H2N H3 N
glycine hydrochloride

In the solid state, amino acids exist as dipolar ions in which the carboxyl group
is present as a carboxylate ion and the amino group is present as an aminium
(NH3+) ion. This dipolar ion form of the molecule is known as a ZWITTERION.

H2C COOH H2C COO–

+
H2N H3N
glycine ionic form of glycine
(a Zwitterion)

4. PEPTIDE FORMATION AND PROTEINS

Amino acids are linked by peptide
bonds. These bonds are formed by a Proteins are the largest and most complicated molecules that exist in the cells of
dehydration synthesis reaction between
living organisms.
the carboxyl group of the first amino
acid and the amino group of the second Proteins are polymers that are formed by many hundreds or even thousands of
amino acid.
amino acid units. These units are bonded together by a peptide linkage.
H O
Peptides are amides formed by the reaction of amino groups with the carboxyl
N C
groups of amino acids. According to the number of amino acid units they are
made up from, they are known as dipeptides, tripeptides or polypeptides.

H O H H O H O H H O

H2NC COH + HN C COH H2NC C N C COH + H2O

peptide
R¢ R¢¢ R¢ linkage R¢¢
a–amino acid a–amino acid dipeptide molecule

208 Oxygen And Nitrogen Containing Organic Compounds

If the number of amino acids forming peptide bonds is “n”, (n–1) molecules of
water are produced in the peptide formation.

H O H H O H H O H H O H H O H H O

H2N C C OH + H N C C OH + H N C C OH + .... (n–1)H2O + N C C N C C N C C

R¢ R¢¢ R¢¢¢ R¢ R¢¢ R¢¢¢

a–amino acid a–amino acid a–amino acid polypeptide

n molecules

If the number of amino acids forming polypeptide bonds is more than 12.000,
the polypeptides are called PROTEINS.

Although proteins contain only 20 kinds of amino acids, they can be arranged in
many different sequences. Consequently, a small number of amino acids may
form many different types of proteins.

Proteins are used for repairing degenerated tissue in living organisms. DNA and
RNA are also proteins.
The DNA helix is a protein.

CHEMISTRY OF VISION

Have you ever wondered how vision occurs in our eyes? cis-retinal, it transforms into trans-retinal.
Many miraculous processes happen in our eyes. For Cis-retinal exists in a protein called rhodopsin. Trans-
good vision to occur, the retina of the eye retinal doesn’t fit into the protein and so a
must sense incoming light. series of changes in the geometry of the
A light image is in fact mapped onto protein begins.
the surface of the retina by activating The new form of protein is
light sensitive cells called rods and bathrhodopsin. During these
cones. changes, the protein undergoes a
Vitamin A is transported to the rods large potential difference. This
in the retina from the liver, and here potential difference is picked up by
it is transformed into a substance a nerve cell as an electrical impulse.
called cis-retinal. The nerve cell carries this impulse to
the brain, where the visual information
The molecule cis-retinal can absorb light
is encoded.
at a visible wavelength. When light strikes

Trans–retinal
Vitamin A Light strikes Cis–retinal
changes the shape nerve impulse is
converts to o cis–retinal o converts to o o
of rhodopsin to carried to brain
cis–retinal in rod cell trans–retinal
bathrhodopsin

Amines, Amides And Amino Acids 209

1. Describe the general structures of amines, amides, 10. Name the following amides.
amino acids, and proteins.
a. CH3 C O b. CH3 C O

CH3 N CH3 CH3 N C2H5

2. Name the following amines and give their types.
O O
CH3 CH3
c. C NH2 d. C3H7 C NH2
a. CH3 C NH2 b. CH3 N CH3

CH3

CH3 11. 5.95 grams of NH3 reacts with excess acetyl chloride
c. CH3 N d. CH3 NH (CH3–CO–Cl). How many grams of acetamide are pro-
duced? (Cl : 35.5 g/mol, O : 16 g/mol, H : 1 g/mol, C :
12 g/mol, N : 14 g/mol)

3. Write the structural formulae of the given amines.

12. N-ethylacetamide is formed by the reaction of ethyl-
a. cyclopropylamine amine and acetylamide. When 9 grams of ethylamine is
b. dimethylethylamine reacted, how many grams of N-ethyl acetamide can be
formed?
c. ethylhexylamine
d. methylethylisopropylamine
13. Compare the chemical properties of amino acids and
amides.
4. What is the mass percentage of nitrogen in cyclopenty-
lamine? 14. Explain why amino acids are generally amphoteric com-
(O : 16 g/mol, H : 1 g/mol, C : 12 g/mol, N : 14 g/mol) pounds.

5. What is the formula of the alkyl in the primary amine of
which 0.2 mole has a mass of 9 grams?
6. Amines show weak basic properties when they are dis-
solved in water. Explain why?
15. 0.2 M of 400 mL NaOH solution reacts with
aminoacetic acid. What mass of salt is formed?
(Na : 23 g/mol, O : 16 g/mol, H : 1 g/mol, C : 12 g/mol,
N : 14 g/mol)
16. Explain how peptide bonds are formed.

7. [H+] is 10–12 M in 0.25 M propylamine solution. What is 17. What is the difference between an amino acid and a pro-
the Kb value of propylamine? tein?

18. What is the molecular weight of the dipeptide obtained

8. 3.4 grams of NH3 reacts with 20.2 grams of CH3Cl. Find
the formula of the amine formed by this reaction and
name it. (Cl : 35.5 g/mol, O : 16 g/mol, H : 1 g/mol,
C : 12 g/mol, N : 14 g/mol)
9. What are the differences between amines and amides in
terms of their structures?
from an amino acid of which 0.1 mole has a mass of 75
grams?
19. How many water molecules are formed when 100 amino
acid molecules are bonded together by peptide bonds?
20. What is the importance of proteins in daily life?

210 Oxygen And Nitrogen Containing Organic Compounds

1. Some compounds and their types are given. Which pair 4. What is the name of the alkyl group in the primary amine
are wrong? that has a molecular weight of 45 grams?

Compound Type A) Methyl B) Ethyl C) Propyl D) Isopropyl E) Aryl

A) R C O amide

NH2

B) R C COOH amino acid

NH2
C) R NH2 primary amine

H O H H
5. Which one of the following is not a secondary amine?
D) H2N C C N C COOH dipeptide

R R A) CH3 NH B) N CH3

CH3 H
E) N R secondary amine

R CH3
N
C) D) CH3 C NH2
H
CH3

E) CH3 N C2 H 5
2. I. CH3 – NH2
H
II. CH3 – OH
III. NH3
Which of the compounds above is (are) basic?

A) I only B) III only C) I and III

D) II and III E) I, II and III

6. I. CH3 N CH3

CH3
3. For an aqueous solution of the H II. CH3 NH2
compound;
H 3C C NH2 O
I. The pH > 7.
CH3 III. CH3 C NH2
II. It conducts electricity.
III. It reacts with Zn metal to give H2 gas. Which of the above compounds undergoes hydrogen
Which of the above statements is (are) correct? bonding with itself?

A) I only B) II only C) I and II A) I only B) II only C) II and III

D) II and III E) I, II, III D) I and III E) I, II and III

Amines, Amides And Amino Acids 211

7. Which one of the following is a primary amide? 10. Which of the statements below is incorrect for 1 mole of
acetamide and 1 mole of N-methylformamide?
O O
A) H C NH2 B) H C N CH3 C) CH3 C NH A) Their carbon atom numbers are equal.

CH3 O CH3 B) The masses of their nitrogen atoms are equal.

O O C) The number of their hydrogen atoms are equal.
D) CH3 C N CH3 E) C2H5 C N CH3 D) They have different number of pi bonds.
CH3 H E) They contain the same number of oxygen atoms.

11. An unknown organic compound forms a dipolar ion (a

Zwitterion) and is optically active. Which one of the given
compounds may be the unknown compound?
O O
8. Which statement is incorrect for D-aminoacids?
A) CH3 C OH B) CH3 C NH2
A) They are not optically active.
B) They contain two kinds of functional groups. CH3 H

C) They form Zwitterions in the solid state. C) CH3 C COOH D) CH3 C COOH

D) They are amphoteric. NH2 NH2

E) They are slightly soluble in water.
E) CH3 C CH3

12. Compound Functional Groups

9. O ——————— ——————————
I. Amine Nitro
CH3 C NH2
II. Amide Carbonyl, hydroxyl
For the above compound, which statement is correct?
III. Amino acid Amino, carboxyl
A) It is named aminoethanoic acid. Nitrogen containing organic compounds and their func-
B) It is optically active. tional groups are given. Which description(s) is (are) cor-
C) It reacts with HCl. rect?

D) It is neutral. A) I only B) III only C) I and II

E) It reacts with NaOH. D) II and III E) I, II and III

212 Oxygen And Nitrogen Containing Organic Compounds

13. Peptide bonds; 15. Some compounds and the properties of their solutions
I. are formed between at least two amino acids. are given below. Which pairing is incorrect?

II. are formed between nitrogen and carbon atoms. Compound Property

III. form Zwitterrions (dipolar ions). A) C2H5 C O Neutral

Which of the above statements is(are) correct? NH2

A) I only B) II only C) I and II B) CH3 CH COOH Amphoteric

D) II and III E) I, II and III NH2

C) CH3 NH Basic

CH3
D) CH3 CH COOH Acidic

OH
E) CH3 CH2 CH COOH Basic

OH

14. Which one of the following compounds is named incor-

rectly?

Compound Name

A) CH3 C NH Propionamide

O CH3

B) CH3 CH2 NH2 Ethylamine

C) CH3 CH COOH a – aminopropanoic acid

NH2

D) NH2 Cyclopentylamine

E) C NH2 Benzamide

Amines, Amides And Amino Acids 213

 CRISS – CROSS PUZZLE
Solve the clues and place your answers in their correct positions in the grid.

1 2 3

CLUES ACROSS CLUES DOWN

2. These compounds are the basic building units of pro- 1. Two carbon containing amide.
teins, which are the basis of living organisms.
2. These are organic compounds derived from ammonia
4. These bonds are formed between two amino acid mol- by replacing a hydrogen with an organic acid groups.
ecules.
3. Because of the existence of both (–NH2) and (–OH)
5. These are weak bases and organic derivatives of groups, amino acids show _____________ properties.
ammonia. They are also known as alkylated ammonia
compounds.
6. These are polyamides and the monomers from which
they are derived are D-amino carboxylic acids. They
are found in all living cells. These compounds contain
more than 12000 polypeptide bonds.
7. If one alkyl group replaces one hydrogen atom in
ammonia these type of amines are formed.

214 Oxygen And Nitrogen Containing Organic Compounds

 1. PHENOLS
Phenols are compounds that have the general formula Ar – OH. In phenols, the
carbon atom to which the –OH group is attached undergoes sp2 hybridization,
so in general, phenols display different properties to alcohols.

Phenols, depending upon the number of – OH groups, can be classified as

mono, di or triphenols. The simplest member of the phenols is phenol itself. The
methyl phenols are known as cresol. Many phenol compounds may be extracted
from coke by distillation.

OH OH OH OH

Phenol is the raw material for the pro- OH OH

duction of many substances, ranging
from aspirin to plastics. CH3 OH
1 –hydroxy – 1,2 – dihydroxy 1,2,3 –trihydroxy
hydroxybenzene 3 – methylbenzene benzene benzene
(phenol) (cresol) (pyrogallol)

Phenols display acidic properties. Both phenols and alcohols contain the –OH
and so they have similar properties to some extent , for example, they can both
be converted into ethers and esters. However, in general, they show very differ-
ent characteristics and must be classified as different families.

OH 1.1. PHENOL
8 1 8 1
OH
7 2 7 Pure phenol is a colorless, crystalline solid with a melting point of 43°C. It is
2

6 3 6 3 hydrated and turns red when exposed to air. It is soluble in water, like alcohols
5 4 5 4
and ethers. Phenol is a poisonous substance and contact with skin causes burns.
1 – naphtol 2 – naphtol
(a – naphtol) ( b – naphtol) Dilute solutions of phenol are used as antiseptics and disinfectants.
9 10
Phenol is widely used as a starting material in the manufacture of nylon, plastics,
8 1
dye stuffs, aspirin and antiseptics.
7
2 OH
In industry, phenol is obtained from coke by distillation though there are various
6 5 4 3

2 – phenantrol ways of manufacturing phenol in laboratories.

Compounds having an –OH group Chlorobenzene reacts with NaOH under high temperature and pressure to pro-
attached to a polycyclic benzenoid ring duce phenol.
are also phenols. They are known as
naphtols or phenantrols. 350 °C
Cl + NaOH OH + NaCl
200 atm

chlorobenzene phenol

216 Oxygen And Nitrogen Containing Organic Compounds

Phenol is more acidic than alcohols (but less acidic than carboxylic acids).

OH COOH
ortho position meta position para position
phenol benzoic acid (o –) (m–) (p–)
Ka = 1 · 10–10 Ka = 6 · 10–5
Indicating the relative positions of sub-
stituents on benzene ring

1. Phenol reacts with NaOH like carboxylic acids whereas alcohols do not,

R OH + NaOH o no reaction

alcohol base

R COOH + NaOH o R COONa + H2O

carboxylic acid base carboxylic acid salt

– +
OH + NaOH O Na + H2O

phenol base sodium phenoxide

2. Phenol does not react with basic salts such as NaHCO3 like alcohols.

R OH + NaHCO3 o no reaction

alcohol basic salt

R COOH + NaHCO3 o R COONa + CO2 + H2O

carboxylic acid basic salt carboxylic acid salt

OH + NaHCO3 ® no reaction.
basic salt
phenol

3. Phenol is converted into 2, 4, 6 – trinitrophenol by concentrated nitric acid in

the presence of H2SO4 catalyst.

OH OH
O2N NO2
H2SO4
+3HNO3
phenol
NO2
2,4,6 – trinitrophenol
(pycric acid)

Aromatic Compounds 217

 4. Phenol can be halogenated by halogens in their aqueous solutions or in a
CS2 solvent.

OH OH
Br Br
H2O
+ 3/2 Br2

phenol
Br
2,4,6 - tribromophenol

OH OH

Br2, CS2 cold

phenol
Br
Leo Hendrik Baekeland p - bromophenol

(1863 - 1944) 5. The most important reaction of phenol is its polymerization reaction with
Leo Baekeland (November 14, formaldehyde, which produces bakelite.
1863 – February 23, 1944) was a
Belgian born American scientist OH OH
who invented bakelite.
CH2 CH2 CH2
Bakelite was made from phenol and OH
formaldehyde by heating them OH
together in a pressure molding. n + n HCHO CH2 CH2
–n H2O
Prior to Baekeland, Adolf von OH
Baeyer had experimented with this phenol formaldehyde
CH2 CH2 CH2
substance but didn’t complete his
work. OH OH

Radios, televisions and electrical bakelite

insulators were made of bakelite
Electrical insulators are made from bakelite because of its insulating and heat-
due to its insulating and heat resist- resistant properties.
ant properties.

2. AROMATIC NITRO COMPOUNDS

2.1. GENERAL STRUCTURE
NO2 NO2 NO2

NO2 O2 N NO2
mononitrobenzene 1,3–dinitrobenzene 1,3,5–trinitrobenzene
m–dinitrobenzene

218 Oxygen And Nitrogen Containing Organic Compounds

The –NO2 group is a meta director. Thus, all other groups after the first –NO2
group are attached to the ring in the meta position.

2.2. NITRATION
The nitration of an aromatic ring, requires a mixture of concentrated sulfuric and
nitric acids. This generates the nitronium ion, NO2+. When benzene is added to
this mixture at room temperature, mononitrobenzene is formed. Hydrogen
atoms in an aromatic ring can only be substituted by a strong electrophile, such
as NO2+.
– + + – +
2H2SO4 + HO NO2
NO2 + 2HSO4 + H3O
nitronium ion
NO2

+ 80°C +
+ NO2 + H

benzene nitrobenzene

The yield of nitration depends upon the concentrations of the acids, temperature
and the length of the nitration process. In the nitration process, a maximum of
three nitronium ions (NO2+) can be attached to the benzene ring since the nitro
group is a meta director. However attaching the third nitro group is very difficult.
The existence of the –CH3 or –OH group on a benzene ring makes nitration easier.

Nitrobenzene
Nitrobenzene is a yellow, oily liquid with a boiling point of 209°C and a charac-
teristic almond smell. The vapor of nitrobenzene is poisonous and it is a carcino-
Nitrobenzene, when inhaled, damages
gen. Nitrobenzene is denser than water and insoluble in it, though it is a good the structure of hemoglobin.
polar solvent itself .
NO2

H2SO4
+ HO NO2 + H2 O

benzene nitrobenzene

Nitrobenzene does not react with acids and bases. It can be reduced to aniline
using the catalysts of Fe, Sn or Zn in acidic solutions.
NO2 NH2

+ 2Fe + 6HCl + 2FeCl3 + 2H2O

nitrobenzene aniline

Nitrobenzene and aniline are both widely used in the dye industry.

Aromatic Compounds 219

Ortho and Para
Dinitrobenzene
Meta Directors
Directors
Dinitrobenzene is prepared by the direct nitration of nitrobenzene. This yields
R
secondary m–dinitrobenzene.
N NO2 nitro
amine group
R
NO2 NO2
NH2 amino SO3H sulpho
OH hydroxyl CN cyanide H2SO4
+ HO NO2 + H2O
OR alkoxy COOH carboxyl NO2
O nitrobenzene m–dinitrobenzene
aldehyde
R alkyl C group
H It is a yellow, crystalline solid with a melting point of 89 °C. It is a slightly polar
O substance, insoluble in water, but soluble in alcohol.
C6H5 phenyl keto
C group
R NO2 NO2 NO2
F, Cl, Br, I NO2
(halides)
NO2
Specific atoms or groups on a ben-
NO2
zene ring give defined directions to any
o – dinitrobenzene m – dinitrobenzene p – dinitrobenzene
further atoms or groups attaching to the
ring.
Ortho and para dinitrobenzene can be produced using alternative methods.

Trinitrotoluene
Toluene is easily nitrated since it has an alkyl (–CH3) group attached to the ben-
zene ring. It can be prepared by direct nitration of toluene with a mixture of nitric
acid and sulfuric acid.

The nitration mechanism is similar to that of the nitration of benzene.

–
HNO3 + 2H2SO4
NO+
2
+ H3O+ + 2HSO4

CH3 CH3
O2N NO2
H2SO4
+ 3HO NO2 + 3H2O

toluene NO2
The explosive known as TNT is trinitro- 2,4,6–trinitrotoluene
toluene.

Trinitrotoluene is a crystalline solid that melts at 81°C. It is widely used as an

explosive (TNT, tritol) in shells and bombs. It is not as sensitive to shock and fric-
tion as other explosives can be.

220 Oxygen And Nitrogen Containing Organic Compounds

 1
Synthesize the following compounds from benzene.
a. o–nitrotoluene
b. m–chloronitrobenzene

a. Methyl (–CH3) is a ortho-para director, and –NO2 is a meta director. –CH3

must be attached to the ring first to obtain an ortho structure.

FeCl3 HNO3/H2SO4
+ CH3Cl – HCl
CH3 – HCl CH3

NO2
benzene toluene o – nitrotoluene

b. We must obtain a meta compound. So a meta director must be first attached

to the ring.
H2SO4 Cl2/FeCl3
+ HNO3 – HCl
NO2 – HCl
NO2

Cl
benzene nitrobenzene m – chloronitrobenzene

3. AROMATIC AMINO COMPOUNDS

Indigo is a dark blue, water soluble dye
H
NH2 CH3 NH2 that has been in use for a long time. The
NH2 N picture shows first the indigo compound
synthesized by Baeyer Laboratories in
1890 .
NH2
aminobenzene 2 – aminotoluene 1,3 – diaminobenzene diphenylamine
phenylamine o – aminotoluene m – diaminobenzene
aniline o – toluidine m – phenylene diamine

Aromatic amines are generally produced by the reduction of nitro compounds.

They have characteristic and pleasant odors. They are soluble in alcohol and
ether but only slightly soluble in water. The basicity of aromatic amines is weak-
er than that of ammonia and aliphatic amino compounds. They form salts with
strong acids.

3.1. ANILINE
Aniline was first synthesized from indigo. Aniline is a colorless liquid with a boil-
ing point of 184 °C. It has a specific odor and is poisonous. If exposed to sun-
light for some time it oxidizes and its color turns to light yellow. Aniline

Aromatic Compounds 221

 It forms acidic anilinium salts (phenyl ammonium) upon reaction with acids.
+ –
C6H5NH2 + HCl o C6H5NH3 Cl
aniline anilinium chloride
phenylamine phenyl ammonium chloride

Anilinium salts can be converted back to aniline by NaOH.

+ – + –
C6H5NH3 Cl + Na OH o C6H5NH2 + NaCl + H2O
anilinium chloride aniline

Preparation
There are two widely used methods to produce aniline.

1. Nitrobenzene is reduced to produce aniline.

Aniline is a colorless liquid. However , The reduction is done using iron and water vapor in industry.
the aniline used in industry has a light
NO2 NH2
yellow color. Aniline and water form two heat
layers when mixed together. Aniline + 2Fe + 4H2O + 2Fe(OH)3
stays below the water because its den-
sity is higher (left tube). Aniline can react nitrobenzene aniline
with HCl solution since it is a weak base In the laboratory, instead of water vapor, acid is used.
(middle tube). If a sufficient amount of + –
HCl is added, a colorless anilinium chlo- NO2 NH3Cl
ride (C6H5NH3+Cl–) is formed (right + 2Fe + 7HCl + 2FeCl3 + 2H2O
tube).
nitrobenzene anilinium chloride

+ –
NH3Cl NH2
+ NaOH + NaCl + H2O

anilinium chloride aniline

While being reduced, nitrobenzene takes six electrons per molecule from the
metal atoms. The electrical charge in the medium is balanced by the protons
(H+) of the acid.
+5 –1
NO2 NH2
– +
+ 6e + 6H + 2H2O

nitrobenzene aniline

2. Aniline can also be produced by the reaction of phenyl halides with ammonia
The anilinium ion (C6H5NH3+) in anilini- under high temperature and pressure.
um chloride shows weak acid proper- Cl NH2
high pressure
ties. If NaOH is added to anilinium chlo- + 2NH3 + NH4Cl
300 °C
ride solution (left tube), the anilinium
ions loses a proton to give aniline (mid- phenyl chloride aniline
dle and right tube)

222 Oxygen And Nitrogen Containing Organic Compounds

4. AROMATIC ALCOHOLS
Compounds that have a hydroxyl group attached to a chain on a benzene ring
are called aromatic alcohols. These alcohols differ from phenols and show sim-
ilar properties to aliphatic alcohols. The most important aromatic alcohols are
benzyl alcohol and E-phenyl ethyl alcohol.

CH2OH CH2CH2OH

benzyl alcohol b – phenyl ethyl alcohol

4.1. BENZYL ALCOHOL

This is the simplest member of the aromatic alcohols. It is isomeric with cresol.

CH2OH CH3

sp3 OH
benzyl alcohol o – cresol

Its oxidation products are benzaldehyde and benzoic acid, respectively.

It is a colorless liquid with a pleasant odor and has a boiling point of 205 °C.

O O
CH2OH C H C OH
[O] [O]
– H2O

benzyl alcohol benzaldehyde benzoic acid

The benzyl alcohol structure contains both the aliphatic and aromatic groups.
Although it is an alcohol, it dissolves in organic solvents and is only slightly solu-
ble in water. It reacts with Na and K to produce H2 as phenols and cresols do.
However, phenols and cresols are differentiated from benzyl alcohol by their reac-
tion with NaOH. Esters of benzyl alcohols also have a nice, pleasant odor.

Preparation
Benzyl alcohol is produced by the same general methods used for the produc-
tion of aliphatic alcohols.

CH2 Cl CH2 OH
H2O
+ NaOH + NaCl
heat

benzyl chloride benzyl alcohol

Aromatic Compounds 223

 Br MgBr H CH2OMgBr CH2OH
Mg + ether +H C O +HBr/ether
+ MgBr2

phenyl bromide phenyl magnesium benzyl alcohol

bromide

2
4.48 liters of H2 gas at STP is produced by the reaction of a 39 gram mixture of
phenol and benzyl alcohol with Na metal. What is the mole percentage of benzyl
alcohol in the mixture? (C6H5OH : 94 g/mol, C6H5CH2OH : 108 g/mol)

4.48L
nH = —————— = 0.2 mol
2
22.4 L/mol
Reactions of phenol and benzyl alcohol with Na;
OH ONa
+ Na + 1/2 H2
x/2
x

CH2OH CH2ONa
+ Na + 1/2 H2
y/2
y

As it is seen, total mole number of H2 gas

x y
—— + —— = 0.2
2 2
And masses of phenol and benzyl alcohol are 94x and 108y respectively. So total
mass equation is written as
94x +108y = 39
Now, by using the above equations x and y can be calculated;
–188 x/2 + y/2 = 0.2
94x + 108y = 39
————————————————
14y = 1.4
y = 0.1 mol
x = 0.3 mol
Then, the mole percentage of benzyl alcohol can be calculated.
0.1 mol
————— . 100 = 25% is benzyl alcohol.
0.4 mol

224 Oxygen And Nitrogen Containing Organic Compounds

5. AROMATIC ALDEHYDES
Aromatic aldehydes are compounds in which the aldehyde functional group
O

( C H ) is directly attached to the benzene ring. The simplest aromatic alde-

hyde is benzaldehyde.
The other aromatic aldehydes show similar properties to benzaldehyde.

5.1. BENZALDEHYDE
Benzaldehyde is a colorless liquid which boils at 179 °C and has a bitter almond The seeds of almonds.
taste and smell. It is found in the seeds of almonds, plums and peaches togeth-
er with glucose and HCN.
It dissolves well in alcohol and ether and is slightly soluble in water. Benzaldehyde
is similar to aliphatic aldehydes in many ways.
It can be reduced by LiAlH4 to benzyl alcohol.
LiAlH4
C O CH2OH
H
benzaldehyde benzyl alcohol

It is oxidized by acidic K2Cr2O7 solution or alkaline KMnO4 solution togive prod-

uct being benzoic acid. Benzaldehyde is a weak reducing agent, it slightly affects The seeds of peaches contain ben-
Tollens’ reagent but does not react with Fehling’s reagent at all. zaldehyde.

+ heat +
C O + 2Ag(NH3)2 + H2O COOH + 2Ag + 2NH4 + 2NH3
H
benzaldehyde Tollens’ reagent benzoic acid

Preparation
There are numerous industrial production methods for benzaldehyde.

1. Benzaldehyde can be produced by the oxidation of benzyl alcohol with air

using hot V2O5 as a catalyst.
V2O5
CH2OH + 1/2 O2 C O + H2O
H

2. Toluene can be chlorinated and the benzalchloride product hydrolyzed.

+2Cl2 H2O
CH3 –2HCl CHCl2 C O + 2HCl
H
toluene benzalchloride benzaldehyde

Aromatic Compounds 225

 3
What mass of benzaldehyde can be produced from 64.4 grams toluene with 60%
efficiency? (C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

Molar mass of toluene Ÿ C6H5CH3 = 92 g/mol

Molar mass of benzaldehyde Ÿ C6H5CHO = 106 g/mol
Moles of toluene
m 64.4 g
n = —— = —————— = 0.7 mol
M 92 g/mol
The reaction is;
O
+2Cl2 +H2O
CH3 –2HCl
CHCl2 C H + 2HCl

Toluene Benzaldehyde

From 0.7 mol of toluene, 0.7 mol benzaldehyde is produced, but since the effi-
ciency is 60%, then,
60
0.7 . ——— = 0.42 mol of benzaldehyde produced.
100
Mass of benzaldehyde = M . n = 106 g/mol . 0.42 mol = 44.52 g

6. AROMATIC CARBOXYLIC ACIDS

Aromatic compounds that have one or more carboxyl groups (–COOH) in their
structure are called aromatic carboxylic acids.

COOH COOH COOH COOH

OH CH3

COOH
benzoic acid m – phthalic acid salicylic acid toluic acid

Aromatic carboxylic acids have boiling points higher than 100°C. They are color-
less solid substances with a crystalline structure. They show similar properties to
aliphatic carboxylic acids but they are only slightly soluble in water due to the
benzene ring. They are more acidic than aliphatic carboxylic acids as the ben-
zene ring increases their acidic character.

226 Oxygen And Nitrogen Containing Organic Compounds

6.1. BENZOIC ACID
This is a solid that melts at 121°C and is soluble in hot water, alcohol and ethers.
It undergoes the same reactions as aliphatic carboxylic acids.

1. It forms benzoyl chloride upon reaction with PCl3, PCl5 or SOCl2

COOH + PCl5 COCl + POCl3 + HCl

benzoic acid benzoyl chloride

2. It forms esters when reacted with alcohols, these products have a pleasant odor.

H+
COOH + C2H5OH COOC2H5 + H2O

benzoic acid ethyl alcohol ethyl benzoate

Preparation
Primary and secondary alkyl groups (but not tertiary) directly attached to a ben-
zene ring may be oxidized by KMnO4.

O
C H
CH3
[O]
[O] benzaldehyde
toluene
O

[O] [O] C CH3

CH2 CH3 COOH

ethylbenzene acetophenone

CH3 [O]
[O]
CH
CH3 CH2OH

isopropylbenzene benzyl alcohol

If the carbon attached to the benzene ring is tertiary, no reaction occurs.

CH3
[O]
C CH3 no reaction
CH3
tert – butylbenzene

Aromatic Compounds 227

 Benzoic acid can also be prepared by the hydrolysis of benzoylchloride and ben-
zonitriles.

O O
heat
C Cl + H2O C OH + HCl

benzoyl chloride benzoic acid

acid
CN + 2 H2O COOH + NH3

benzonitrile benzoic acid

6.2. TEREPHTHALIC ACID

Terephthalic acid, also called paraphthalic acid or 1,4–benzene dicarboxylic acid,
is an aromatic dicarboxylic acid.

KMnO4 / OH –
H3C CH3 HOOC COOH

p – xylene terephthalic acid

Dicarboxylic aromatic acids form polymers by reacting with dialcohols such as

glycol.

Polyethylene terephthalate can be obtained by a direct acid - catalyzed esterifica-

tion. It is also known as Dacron, Terylene or Mylar.

–(n–1)H2O
n HOOC COOH + n HO CH2 CH2 OH

terephthalic acid glycol

OC COO CH2 CH2 O

n
dacron (terylene)
Polyethylene terephtalate (PET)

228 Oxygen And Nitrogen Containing Organic Compounds

1. Write out the structural formulae of the given compounds 10. Compare the boiling points of the isomers of dinitroben-
a. nitrobenzene zene.
b. o-nitrotoluene
c. m-dinitrobenzene 11. Classify the following atoms and groups as ortho, meta
or para directors.
d. 2, 4, 6 - trinitrotoluene
a. methyl (–CH3) b. chloro (–Cl) c. ethyl (–CH2CH3)
e. 4-chloro-2,3-dinitrotoluene
d. amino (–NH2) e. nitro (–NO2) f. hydroxyl (–OH)

2. Name the following compounds

12. Write out the structural formulae of the given com-
a. NO2 b. O2N NO2 pounds.
a. aniline b. diphenylamine
CH3
c. anilinium bromide d. 2-amino-4-nitrotoluene
CH3
e. p-toluidine f. methyl-diphenylamine
Br
c. NO2 d. O2N NO2 13. Name the following compounds
a. NH2 b. H2N NH2
CHCH3
CH3 CH2Cl
CH3
CH2CH3

3. What is the function of H2SO4 used in the nitration of

c. NH2 d. O2N NH2
benzene? Explain.

4. When nitrobenzene is nitrated with nitric acid and sulfu-

ric acid, to which position will the nitro group attach? H3 C C CH3 CCl3
Explain why? CH3

5. During nitration, what factors determine the number of

–NO2 groups able to attach to the aromatic ring? 14. Compare the following compounds with respect to their
basicity.
I. P(OH)3 II. NH3 III. CH3NH2 IV. C6H5NH2
6. Nitration of toluene is easier than that of benzene.
Explain why?
15. Which of the following compounds are solids at room
7. What is TNT? What is it used for? temperature?
a. nitrotoluene b. m-dinitrotoluene
c. trinitrotoluene d. aniline
8. Calculate the molar mass of trinitrotoluene?

9. Starting from benzene, how is p–bromonitrobenzene 16. Why can not the amino (–NH2) group be attached to the
produced? aromatic ring directly?

17. Prepare aniline starting from nitrobenzene. Balance your

Br NO2 equation(s).

Aromatic Compounds 229

18. 0.3 mol of 2,6–diaminotoluene is obtained by reducing 27. Name the following compounds.
2,6–dinitrotoluene with iron dust.
a. CH2OH b. CH2CH2OH
In this reaction;
a. how many moles of 2,6–dinitrotoluene are used?
b. how many grams of Fe dust are consumed?
c. how many mL of 0.5 M HCl solution are used up? c. CH2OH d. CH3
C OH
19. 100 mL of 0.5 M H2SO4 is used to neutralize the aniline CH3
obtained from 24.6 grams of nitrobenzene. Use this OH
information to find the efficiency of the reduction reac-
tion of nitrobenzene to aniline?
28. Write the structural formulae of the following com-
pounds.
20. Write the reduction reaction of m-dinitrobenzene with Zn
a. benzyl alcohol
dust and HCl and name the products.
b. p–methylbenzyl alcohol
c. 1– phenyl–2–methyl–1–propanol
21. Define the phenol compounds. What are the differences
between alcohols and phenols? d. m-trichloromethylbenzyl alcohol

29. What is the difference between benzyl alcohol and cresol?

22. Write the structural formulae of the following compounds.
a. phenol b. m–cresol
30. A compound having the molecular formula C7H8O
c. 2,4,6–trichlorophenol d. 2–bromo–5-methylphenol
changes color in FeCl3 solution. When it is oxidized, ben-
e. m–bromophenol f. pyrogallol
zoic acid is produced. What is the structural formula of
this compound?
23. Name the following compounds.
Br
a. b. 31. Write the reaction equations of benzyl alcohol with the
OH OH following substances and name the products.
a. potassium
OH Br Br b. acetic acid (in H2SO4 medium)
c. phosphorus trichloride (PCl3)
CH3
c. d.
NO2 HO OH
32. Starting from benzene, show how benzyl alcohol may be
HO CH3 produced.
OH
33. Name the following compounds.

24. Why does phenol show acidic properties? a. CHO b. CHO

25. Compare the given compounds with respect to their CH3

acidity.
c. Br CHO d. Cl CHO
I. ethyl alcohol, II. water, III. phenol, IV. aniline

26. Which of the compounds, phenol, acetic acid and ethyl

alcohol, react with NaOH but not with NaHCO3? OH NH2

230 Oxygen And Nitrogen Containing Organic Compounds

34. Write the structural formulae of the following com- 41. Arrange the compounds in increasing order of acidity.
pounds.
I. H3C C6H4 OH
a. benzaldehyde
b. benzoyl chloride
II. H3C C6H4 COOH
c. D–phenylacetaldehyde
d. D–bromophenylacetaldehyde
e. diphenylketone III. H3C C6H4 CH2OH

f. acetophenone

42. I. HOOC(CH2)4COOH
35. Write two different production reactions to show how II. HOOC C6H4 COOH
benzaldehyde can be formed from acetaldehyde.
III. C6H11COOH
Compare the compounds above with respect to their
36. Which of the following compounds oxidize(s) benzalde- acidity.
hyde to benzoic acid? Write the equations.
a. Acidic K2Cr2O7 solution 43. How could you differentiate between benzoic acid and
phenol?
b. Alkaline KMnO4 solution
c. Tollens’ reagent
44. Explain why benzoic acid is a weaker acid than acetic acid.
d. Fehling’s reagent
45. 8.96 liters of O2 gas at STP are consumed in the catalyt-
ic oxidation of toluene to benzoic acid.
37. How many grams of benzaldehyde with excess Tollens’
reagent need to be used to precipitate 43.2 grams of Ag. a. How many grams of toluene are used up in this reac-
tion?
b. How many milliliters of 0.4 M benzoic acid solution
38. Starting from benzene, show all steps in the production are produced?
of benzaldehyde.
46. CH2Cl
heat
+ NaOH(aq) H2O
X + NaCl
39. Write the structural formulae of the given compounds.
a. benzoic acid b. o–phthalic acid H
c. terephthalic acid d. salicylic acid CHCl2 C O
heat
+ Y + 2HCl

40. Name the following compounds

a. COOH b. COOH CCl3 COOH

heat
+ 2 H2O + 3Z
OH

c. H3C COOH d. Cl COOH What are the substances represented by X, Y and Z in

the above reactions?

47. Which compound must be oxidized to produce ortho

OH COOH phthalic acid? Write the reactions.

Aromatic Compounds 231

1. How many sigma bonds are there in one molecule of 5.
nitrotoluene? NH2

A) 9 B) 10 C) 12 D) 15 E) 17 CH3

Which one of the following is the incorrect name for the

above compound?

A) m-aminotoluene
B) m-toluidine
C) m-methylaniline
2. Which of the following processes is a reduction reaction?
D) m-aminomethylbenzene
A) production of aniline from nitrobenzene. E) p-methylnitrobenzene
B) production of phenylchloride from benzene.
C) production of nitrobenzene from benzene.
D) production of benzoic acid from toluene.
E) production of benzoic acid from benzaldehyde.

6. Which one of the following groups cannot be directly

attached to the benzene ring?

A) –NO2 B) –NH2 C) –OH D) –Cl E) –Br

3. AlCl3
I. C6H6 + Cl2 o
II. C6H6 + Br2 (aq) o
H2SO4
III. C6H6 + HNO3 o
7. Which one of the following compounds is an oxidation
Which of the above reactions actually occur? product of 2,6-dihydroxyaniline?

A) I only B) I and II C) II and III NH2 NO2

D) I and III E) I, II and III A) OH OH B) CHO

CHO

NO2 NH2
C) COOH D) HOOC COOH

4. How many grams of 63% by mass HNO3 must be used COOH

to convert 27.6 grams of toluene to trinitrotoluene in the
NO2
presence of H2SO4?
E) HO OH
(N : 14 g/mol, C : 12 g/mol, H : 1 g/mol, O : 16 g/mol)

A) 60 B) 70 C) 80 D) 90 E) 100

232 Oxygen And Nitrogen Containing Organic Compounds

8. How many mL of 0.8 M HCl solution is needed to neu- 12. Both phenol (C6H5OH) and ethanol (C2H5OH) can react
tralize the aniline that is produced from 49.2 grams of with;
nitrobenzene with 25% efficiency? I. Na metal
(N : 14 g/mol, C : 12 g/mol, H : 1 g/mol, O : 16 g/mol) II. HBr solution
A) 100 B) 125 C) 150 D) 250 E) 500 III. NaOH solution
Which of the above statements is(are) correct?

A) I only B) II only C) I and II

D) I and III E) II and III
9. Which one of the following changes the color of litmus
paper to blue?

A) CH3OH B) CH3 C O C) NH2

13. Which of the combinations below shows the given com-
OCH3 pounds in order of increasing acidity?

I. CH3COOH
D) OH E) HO OH
II. CH COOH
2

Br

III. C6H5OH

10. 1 mol of which of the following compounds can produce A) I > II > III B) III > II > I C) I = II > III
2 mol of CH3COOH? D) II > I > III E) III > I > II

A) B) CH2 OH C)
NH2 OH
CH2 OH

NO2 OH 14. Which one of the given compounds can react with Na,
NaOH and NaHCO3?
D) E) CH3 NH CH3
OH A) C6H5CH2OH B) C6H5OH C) CH3OH
D) HOCH2CH2OH E) C6H5COOH
NO2

15.
A phenylmagnesium B benzyl
11. Compound Preparation Method Bromobenzene o bromide o alcohol
——————— —————————————————
I. nitrobenzene nitration of benzene
What are the reagents A and B?
II. aniline reduction of nitrobenzene
A B
III. phenol addition of base to benzylchloride ——————————— ———————————
A) phenol benzaldehyde / H2O
Which of the preparation methods given above is(are)
B) magnesium bromide acetone/HBr
correct?
C) magnesium formaldehyde/HBr
A) I only B) III only C) I and II D) magnesium acetaldehyde/H2O
D) I and III E) I, II and III E) magnesium bromide formaldehyde/HBr

Aromatic Compounds 233

16. When 1 mole of C7H8O reacts with Na, 0.5 mole of H2 20. Which one of the following is not an isomer of the oth-
and an unknown compound are produced. In addition, ers?
when it is oxidized, salicylic acid is formed. Which one of
CH2OH CH3 CH3
the compounds below must be of C7H8O? A) B) OH C)
A) m–cresol B) Benzyl alcohol
C) o-dihydroxybenzene D) Phenol
OH
E) Phenylmethyl ether OCH3
CH3
D) E)

CHO

17. Benzaldehyde can react with;

I. K2Cr2O7/H+
II. Tollens’ reagent
21. O
III. Fehling’s reagent FeCl3
I. X + CH3 C Y + HCl
IV . LiAlH4
H
Which of the reagents above is(are) correct?
OH
A) I only B) I and IV C) I, III and IV Ni
II. Y + H2 C6H5 CH CH3
D) I, II and IV E) IV only
Which one of the following statements is correct for the
reactions given above?

A) X is benzyl chloride.
B) Y is an aromatic aldehyde.
18. I. Phenol C) The first reaction is an oxidation reaction.
II. Benzoic acid D) The second reaction is an addition reaction.
III. Benzyl alcohol E) The molar mass of X is greater than that of Y.
Which of the above compounds can react with at least
two substances from K, KOH and KHCO3 ?

A) I only B) II only C) I and II

22. Which one of the following is benzyl chloride?
D) I and III E) II and III
O
A) Cl B) C
Cl

C) CH2Cl D) CHCl2
19. How many liters of H2 are produced at STP when 200
grams of 5.4% by mass benzyl alcohol solution reacts
Cl
with Na metal?
E)
A) 1.12 B) 2.24 C) 3.36 D) 4.48 E) 5.6

234 Oxygen And Nitrogen Containing Organic Compounds

23. 26. Which one of the statements given O
AlCl3
+X Y + HCl below is wrong for the compound on C
the right? O
OH
C
Y + H2 CH CH3
O

What are the substances X and Y in the above reactions? A) It is a benzoic anhydride.

X Y B) When 1 mole is hydrolyzed, 2 moles benzoic acid are

———————— ————————————
produced.
A) Acetyl chloride Phenylmethyl ketone
B) Acetic acid Acetophenone C) It is produced by the reaction of benzoic acid with
benzaldehyde.
C) Acetyl chloride Phenylmethyl ester
D) Benzoic acid Phenylmethyl ketone D) The pH value of its solution is less than 7.

E) Benzyl chloride Acetophenone E) When 1 mole reacts with 1 mole NH3, 1 mole ben-
zoic acid and 1 mole benzamide are produced.

27. The compound shown on the right can COONa

be called;
I. sodium-2-hydroxybenzoate
II. sodium m-hydroxybenzoate OH
III. sodium salicylate
24. Which one of the following is the weakest acid? Which of these names is(are) correct?

A) H2SO4 B) CH3CH2OH C) CH3COOH A) I only B) I and II C) III only

D) II and III E) I, II and III
D) COOH E) H3C OH

COOH

28. For the compound OCH2COOH ,

I. CO2 is released when it reacts with NaHCO3.

25. How many pi (S) bonds are there in one molecule of the
compound that is produced by oxidizing o-xylene?
II. Phenol and bromoacetic acid are produced by its
reaction with HBr.
III. When it is hydrolyzed, benzyl alcohol and acetic acid
are produced.
Which of the above statements is(are) correct?

A) I only B) I and II C) I and III

A) 1 B) 2 C) 3 D) 5 E) 6
D) II and III E) I, II and III

Aromatic Compounds 235

29. Which one of the following does not produce benzoic 32. Which one of the following compounds cannot be oxi-
acid when it is oxidized? dized to benzoic acid?

O A) Toluene B) Benzylalcohol C) Benzaldehyde

A) CH2OH B) C
D) Acetophenone E) Tert-butylbenzene
H

C) CH3 D) CH2CH2CH3

CH3

E) C CH3
CH3

33. CH3 is heated with alkaline KMnO4,

the product is then reacted with a strong acidic solution.

Which product will be produced by this process?

A) OH B) CH2OH
30. I. CH3COOH

II. CH3CH(OH)CH3
C) CH2OH D) C O
III. C6H5OH
H
Which of the above compounds can react with Na to OH

produce H2 gas?
E) COOH

A) I only B) I and II C) I and III

D) II and III E) I, II and III

31. Which one of the following compounds does not show

34. Compound Oxidation Product
acidic properties? —————— ——————————
I. Aniline nitrobenzene
OH COOH CH3
II. Toluene benzaldehyde
A) B) C)
III. p-xylene terephthalic acid
OH
Which of the above pairings are correct?
NH3Cl NO2
D) E) A) I only B) I and II C) I and III
D) II and III E) I, II and III

236 Oxygen And Nitrogen Containing Organic Compounds

35. For the compound HO C O 38. O
OH C
I. It is an alcohol. O CH3
II. It is an ester.
By which one of the reactions below may the above
III. It is a hydroxy acid. compound be formed?
Which of the descriptions above are incorrect?
O
A) I only B) II only C) III only A) + CH3 O C

D) I and II E) I, II and III Cl

O
B) C + CH3 OH
H
O
C) C + CH3 ONa
Cl
O
36. For the compound; OH D) Cl + CH3 C
OH
O
CH3 E) OH + CH3 C
I. It reacts with NaOH. Cl
II. When it is oxidized, salicyclic acid is formed.
III. It changes the color of aqueous Br2 solution.
Which of the statements above is(are) correct?

A) I only B) I and II C) I and III

D) II and III E) I, II and III

39. I. C6H5COOH
II. C6H5CHO
37. Initial Substances Polymer Produced
———————————— ——————————
III. C6H5 OH
I. Phenol-formaldehyde Bakelite
IV. C6H5 NH2
II. Terephthalic acid-glycol Dacron
III. Aniline-phenol Acetophenone
Which of the above compounds forms a basic salt with
Which of the pairings above are correct? NaOH and has an aqueous solution that is acidic?

A) I only B) I and II C) I and III A) I only B) I and III C) IV only

D) II and III E) I, II and III D) I and IV E) I, II and III

Aromatic Compounds 237

 CRISS – CROSS PUZZLE
Solve the clues and place your answers in their correct positions in the grid.

1 2

CLUES ACROSS CLUES DOWN

3. It is a colorless liquid with a boiling point of 184°C. It
has a characteristic odor and is poisonous. If it is
exposed to sunlight for some time it oxidizes and its
color turns to light yellow.
5. It is a colorless liquid that boils at 179°C and has a bit-
ter almond taste and smell. It is found in the seeds of
almonds, plums and peaches together with glucose
and HCN.
6. It is a dark blue, water soluble dye which has been in
use for a long time. It was first synthesized by Baeyer’s
Laboratories in 1890 .
7. These are compounds having the general formula
ArOH.
1. Compounds that have one or more carboxyl groups
(–COOH) in their structure, are called aromatic
_____________ acids.
2. It is a heat-resistant compound. Electrical insulators are
made from this because of its insulating and heat-
resistant properties.
4. It is a crystalline solid that melts at 81°C. It is widely
used in explosives.
7. Polyethylene terephthalate.

238 Oxygen And Nitrogen Containing Organic Compounds

 GLOSSARY
Alcohol : Compounds in which the hydroxyl group is
bonded to an alkyl group.
Acetaldehyde (ethanal) : Colorless liquid with a charac-
teristic odor.
Acetic acid : Colorless liquid with a pungent irritating
odor, CH3COOH.
Acid anhydrides : Substances formed the elimination of
one or more molecules of water from two molecules of an
acid.
Acidic strength : The strength of an acid is measured by
the value of its dissociation constant.
Aldehyde : Organic compounds with the carbonyl group
joined directly to another carbon atom.
Alkaloid : Another name for amines.
Amides : Organic compounds derived from ammonia by
the substitution of a hydrogen atoms by an organic acid
group.
Amines : Organic compounds derived from ammonia by
the replacement of one or more of its hydrogen atom by
hydrocarbon groups.
Amino acids : An important class of organic compounds
containing both the carboxyl, — COOH, and the amino,
— NH2 , group.
Aniline : C6H7N, a colorless oily liquid turning brown on
oxidation.
Azeotropic mixture : Mixtures of liquids when distilled
reach a stage at which the composition of the liquid is the
same as that of the escaping vapor.
240 Oxygen And Nitrogen Containing Organic Compounds
Benzaldehyde : C7H6O2, a colorless liquid.
Carbohydrates : Polyhydroxyaldehydes or polyhydroxy
ketones or substances that yield these by hydrolysis. They
are obtained from plants or animals.
Carbonyl group : A type of group containing carbon–oxy-
gen double bond,
Carboxylic acid : Organic compounds containing one or
more carboxy (— COOH) groups.
Cellulose : (C6H10O5)n. The chief constituent of the cell
walls of all plants and the most abundant organic sub-
stance found in nature.
Chirality : A term which may be applied to any asymmet-
ric object or molecule.
Combustion reaction : The reactions in which reactants
burn in an excess of oxygen to form carbon dioxide and
water. These are exothermic reactions.
Dehydration reactions : The elimination of water from a
larger molecule.
Detergents : Water-soluble, surface-active agents capable
of wetting a variety of surfaces and removing greasy and
oily deposits, retaining the dirt in suspension to be rinsed.
Disaccharides : Carbohydrates that may be hydrolyzed to
produce two monosaccharides molecules.
Dextrins : Intermediate products formed during the
hydrolysis of starch to sugars.
DNA : Deoxyribose nucleic acid. It is found in the nuclei of
all cells. It carries the necessary hereditary information that
enables highly specific proteins to be constructed.
Enantiomer : Stereoisomers whose molecular structures
are non-superimposable mirror images.
Esterification : Organic reactions involving the union of
an acid and an alcohol with the elimination of water.
Esters : Organic compounds formed by the union of an
acid and an alcohol with the elimination of water.
Ethers : Compounds in which both hydrogens of water
are replaced by alkyl groups.
Fats : Fats are esters of fatty acids and glycerol.
Fatty acid : Long chained carboxylic acids produced by
the hydrolysis of a lipid.
Fehling’s solution : A solution of copper sulphate, sodi-
um potassium tartrate and NaOH used for detecting
reducing sugar and aldehydes.
Fermentation : Carbohydrates are converted into simple
sugars which are then, they are converted into alcohol and
carbon dioxide.
Formaldehyde (methanol) : HCHO. A colorless gas with
a characteristic and pungent odor.
Formic acid : A colorless liquid which fumes slightly and
has a penetrating odor.
Fructose : C6H12O6. Crystallizes in large needles. The
most common ketose sugar.
Glycerine (Glycerol) : The simplest trihydric alcohol.
Glycogen : (C6H10O5)x. The carbohydrate reserve of the
animal cell.
Glycol : Alcohols containing two – OH groups are called
glycols.
Grignard reaction : When alkyl and aryl halides, particu-
larly bromides and iodides, react with magnesium in the
presence of dry ether to form compounds of the type
RMgX where R represents the alkyl or aryl radical and X the
halide.
Hydrogenation : A specific method of reduction in which
hydrogen is added to a substance directly.
Hydrolysis : A term is used to signify reactions involving
water as a reactant.
Hydroxy acid : Carboxylic acids that contain (— OH)
hydroxyl groups.
Indigo : C10H10N2O2 . A very important and long known
dyestuff.
Keto acids : Carboxylic acids that have the carboxyl group
in their structure.
Ketones : An organic compound containing the carbonyl
group bonded to hydrocarbon groups.
Lactose : C12H22O11. Milk sugar, present in the milk of all
animals.
Maltose : C12H22O11. A disaccharide that is present small
quantities in barley grains and some other plants.
Margarine : Manufactured food product used in place of
butter. Produced from vegetable oils and contains some
polyunsaturated fats.
Markovnikov’s rule : When a reagent containing hydro-
gen adds to an unsymmetrical double bond, hydrogen
adds to the double bonded carbon atom that bears the
greater number of hydrogen atoms.
Monohydric alcohol : Alcohols containing only one
hydroxyl group.
Oxygen And Nitrogen Containing Organic Compounds 241
Monosaccharides : Carbohydrates that cannot be
hydrolyzed into smaller carbohydrates.
Neutralization reaction : The reaction of an acid with a
base.
Nitrobenzene : C6H5NO2. A colorless, highly refractive
liquid with a characteristic smell.
Optical isomers : Stereoisomers that rotate the plane of
plane polarized light.
Optically active : The ability of a compound to rotate the
plane of plane polarized light.
Oxyacid : Organic acids that have a hydroxyl group as
well as a carboxylic group.
Peptide : Substances composed of two or more amino-
acids. Designated as di–, tri–, oligo–, or poly– peptides
according to the number of amino-acids linked by the pep-
tide bond.
Phenols : C6H6O colorless and crystalline and, miscible
with water in all propontions.
Photosynthesis : The process by which green plants build
up their carbon compounds from atmospheric carbon
dioxide and water using light as the energy source.
Polyhydric alcohol : Alcohols with two or more hydroxyl
groups.
Polysaccharides : Carbohydrates with a very high molec-
ular weight (C6H10O5)n. Polysaccharide molecules can be
hydrolyzed into hundreds of monosaccharide molecules.
Proteins : A macromolecular substance found in cells
consisting wholly or mostly of one or more polypeptides,
often combined with another organic molecule or a metal
ion.
242 Oxygen And Nitrogen Containing Organic Compounds
RNA : Ribonucleic acid are found mainly in the cytoplasm.
They are polynucleotides.
Saccharose : (Sucrose) C12H22O11. Cane or beet sugar.
Saponification : The alkaline hydrolysis of an ester into an
alcohol and alkali metals carboxylic acid salt.
Starch : (C6H10O5)n. This carbohydrate is being continu-
ously formed and broken down in living cells and in an
energy reserve.
Terephthalic acid : C8H6O4. Crystallizes into colorless
needles. It is manufactured by the oxidation of p-xylene
and used in the production of terylene.
The Williamson method: This method is used in the
presence of a basic catalyst to produce both symmetrical
and unsymmetrical ethers.
Tollens’ reagent : An ammoniacal solution of silver oxide,
used as a test for aldehydes and result in the deposition of
a silver mirror on the inside of the reaction container.
Trinitro toluene (TNT) : This important explosive is man-
ufactured by the nitration of toluene in several steps,
C7H5(NO2)3 .
Urea (Carbamide) : CH4N2O, (H2N)2 C=O. A colorless
crystalline solid. A weak base that forms salts with strong
acids.
Wood alcohol : Methyl alcohol. It is prepared by the distil-
lation of wood at high temperature.
X rays : Streams of very high energy photons emitted by
substances when bombarded with high energy electron
beams.
 SUPPLEMENTARY Q UESTIONS

Chapter_1 ALCOHOLS AND ETHERS

1. a. CH3 CH OH 16. 11.1 g

CH3 19. a. 2CO2 + 3H2O

c. OH c. CH3OK + 1/2H2

e. CH2 CH2 d. C2H5OI + H2O

OH OH e. CH3CH2CHOHCH3
CH3 f. HCOOCH3 + H2O
g. CH3 CH2 C C CH3 g. CH3CH2CH2 O CH3 + HBr
C2H5 OH
C2H5 C2H5
i. CH3 CH CH2 CH2 OH
i. C3H7 C OMgCl C3H7 C OH
OH
j. CH2 CH3 CH3
CH CH2 CH2OH
k. 3CO2 + 12H2O
2. a. 2 – butanol
c. 5 – methyl – 1 – hexanol 20. 87.5%
e. 3 – ethyl – 3 – pentanol 23. a. Ethoxy ethane, diethyl ether
g. 1,2,3 – propantriol c. 2–isopropoxy propane, diisopropylether
i. p – hydroxy benzyl alcohol e. Cyclopentoxy cyclo pentane, dicyclopentyl ether
3. III > I > II 24. a. CH O CH CH3
3
4. a. CH3 CH2 CH2OH b. CH3(CH2)3OH CH3
n – propanol n – butanol
b. C2H5 O
CH3 CH CH3 CH3 CHOHCH2CH3
2 – butanol
OH c. C3H7 O C3H7
2 – propanol CH3 CH CH2OH
d. CH2 CH O CH CH2
CH3
iso – butanol
25. CH3OCH3 35. a. C4H9 — O — C4H9 ,
6. a. tertiary b. secondary c. secondary d. tertiary dibutyl ether
26. 81.1%
10. 2.24 L 36. a. C2H5OH
27. 36%
11. C5H11OH b. OH
28. 60 g/mol
12. a. 46 g/mol b. ethylalcohol
33. a. Diethyl ether
13. C3H7COOH, 8.8 g c. Methyl vinyl ether 37. II > I > IV > III
34. a, d, e and f
14. 66 g

Oxygen And Nitrogen Containing Organic Compounds 243

 Chapter_2 ALDEHYDES AND KETONES
1. a. 2–chloro propanal 6. O
c. 2,2–dichloro butanal b. C5H8O CH3 CH2 CH CH C
e. 3–chloro butanal
H

2. a. 3–methyl–3–phenyl butanal O
CH3 CH CH CH2 C
b. 3,4–dihydroxo butanal
H
c. 3–methyl–4–bromo–2–butene–1–al
O
d. 2,2–dimethyl propanal
CH2 CH CH2 CH2 C
e. 6–cyano hexanal
H

3. O
O
CH3 CH C C
a. CH3 CH2 C
CH3 H
H
O
O
c. CH3 CH2 CH CH2 C
C
H
OH H
O
e. CH3 CH2 CH C
H 7. a. CH3CH2CH2
Br OH , propanol
f. H
b. CH3 CH CH2 CH3 , 2–butanol
C O
OH
OH c. CH CH2 CH3 , 1–phenyl propanol

d. CH3 CH CH CH2 CH3 , 4–methyl–3–pentanol

4. a. C5H8O CH3 OH
c. C7H5NO3
e. C6H12O3
f. C6H11BrO

5. a. HCHO, formaldehyde, methanal

b. CH3CHO, acetaldehyde, ethanal
c. C2H5CHO, propionaldehyde, propanal

244 Oxygen And Nitrogen Containing Organic Compounds

8. a. Ethenal
b. 2,2–dimethyl propanal
c. 2–methyl butanal
d. 2–methyl propanal

9. 75%

10. 58 g/mol

11. C5H10O

12. Aldehyde, ether and alcohol

14. I > II > IV > III

16. C2H5CHO, 58 g/mol

17. 14.08 g, CH3CHO

18. [O]
b. CH3CHO o CH3COOH
[O]
d. CH3CH2CHO o CH3COOH

19. OC2H5
O
b. CH3 CH C + C2H5OH CH3 CH C OH
H
CH3 CH3 H

CH3 CH3 OH
O
d. CH3 CH C + H 2O CH3 C C OH
H
CH3 CH3 H

20. 20 g propanol

21. a. CH2 OH

CH2 OH

b. O
CH

CH2 OH

22. X: C2H5Br
Y: C2H5OH

Oxygen And Nitrogen Containing Organic Compounds 245

23. 11 g of acetaldehyde
+2H2O +H2O
CaC2 o C2H2 o CH3CHO
–Ca(OH)2

26. a. CH3CHO acetaldehyde

b. 24.75 g

27. (COOH)2, 90 g/mol

28. a. 3–methyl–2–butanone (methyl isopropyl ketone)

b. 4–hydroxo pentan–2–one
c. Cyclopentanone

d. 4–ethyl hexa–1,5–dien–3–one

e. Diphenyl ketone

29. b. CH3 CH CH3 + K2Cr2O7 + 4H2SO4 3CH3 C CH3 + K2SO4 + Cr2(SO4)3 + 7H2O

OH O
OH
H+
d. CH3 CH2 C O + H2 O CH3 CH2 C OH

H H

30. i. CH3 C CH2 CH2 CH3

O
ii. CH3 CH2 C CH2 CH3

O
CH3
iii. CH3 C CH CH3

31. b. 2–propanone
c. Propanal, CH3CH2CHO is isomer of acetone.
Acetone has no isomer as ketone.

32. O
d is an aldehyde. Because it has C H as a functional group.

246 Oxygen And Nitrogen Containing Organic Compounds

 Chapter_3 CARBOXYLIC ACIDS

3. a, b, f 11. a. Acetic acid

c. Butyric acid
5. C3H5COOH

6. a. Monocarboxylic acid – amino acid

b. Dicarboxylic acid – hydroxy acid 12. a. Ethanedioic acid
c. Dicarboxylic acid – oxyacid b. 2–oxypentanoic acid
d. Monocarboxylic acid – keto and hydroxy acid c. 1,3–propandioic acid

7. CH3 CH2 CH2 CH2 COOH pentanoic acid

16. II > I > III
CH3 CH2 CH COOH 2–methyl butanoic acid

CH3
23. a. 0.6%, b. 1.8 · 10–5
CH3 CH CH2 COOH 3–methyl butanoic acid

CH3
24. pOH = 10.6
CH3

CH3 C COOH 2,2–dimethyl propanoic acid

25. 0.36 mol
CH3

26. 0.025 M
8. a. 2–chloro–5–methyl benzoic acid / m–chloro–o–methyl benzoic acid
c. 4–chloro–3–methyl pentanoic acid / J–chloro–E–methyl valeric acid
27. A : CH3CH2Br
B : CH3CH2CN
9. b. 2–methyl–1,5–pentandioic acid
C : CH3CH2COOH
d. 4–cyano–2–pentenoic acid
D : CH3CH2 C Cl

O
10. b. CH3 CH CH COOH

CH3 CH3 29. a. Acid anhydride

c. Hydroxynitrile
d. CH3 CH2 CH CH CH2 COOH

CH3 OH
31. b. CH3 CH COOC2H5 + H2O
C2H5 COOH
e. C C CH3

H H COOC2H5
d. + 2H2O
f. COOH COOC2H5

CH3

j. HOOC CH2 CH COOH

CH3

Oxygen And Nitrogen Containing Organic Compounds 247

32. b. (C2H5COO)2Zn + H2 45. 17.25 g

O O 46. 107.25 g
d. C2H5 C O C C3H7 + H2
48. a. 0.95%
O
49. 0.116 L
f. C3H7 C Cl + H2

COO
50. 115.94 mL
h. Ba + 2H2O
COO 51. 0.3 mol

33. b. 2CH3COOH + Mg(OH)2 o (CH3COO)2Mg + 2H2O 52. 1568 ml

H+
e. CH3COOH + C2H5OH o CH3COOC2H5 + H2O
g. 3CH3COOH + PCl3 o 3CH3COCl + H3PO3
P
i. CH3COOH + Cl2 o CH2COOH
–HCl
I
Cl

34. a. C6H5COOH + Na o C6H5COONa + 1/2H2

b. C6N5COOH + CH3OH o C6H5COOCH3 + H2O
c. C6H5COOH + PCl5 o C6H5COCl + POCl3 + HCl

35. (C2H5COO)2Mg

36. a. Acetyl chloride. b. Calcium acetate

37.
b. COONa

d. (COO)2Mg
CH2 O
f. Ca
CH2 O

h. (C17H35COO)2Zn

j. CH3COOK
l. (COO)2Ca
41. a. C6H5COCl + NaOH C6H5COOH + NaCl

b. CH3 CH2 COOC2H5 + KOH C2H5 COOK + C2H5OH

c. CH3COONa + HBr CH3COOH + NaBr

d. HCOOH + PCl5 HC Cl + POCl3 + HCl

248 Oxygen And Nitrogen Containing Organic Compounds

 Chapter_4 ESTERS

3. a. 120°C 7. CH3 COOH and OH

4. a and d OH
8. O +
H
5. a. methyl acetate a. O CH2 CH2 CH2 C O + H2O

c. phenyl acetate OH
d. 2–bromo ethyl formate O
O H
+

e. 2–butenyl acetate b. O CH2 CH2 CH2 CH2 C OH + H2O

f. isobutyl methyl ester OH
h. isopropyl ester
i. chloromethyl cyclopentyl ester 9.
O
6. O clyst
CH3 C O CH CH3 + H2 CH3 CH2 OH + OH CH CH3
b. C2H5 C O CH2 CH CH3
CH3 CH3
CH3
O 12. a. HCOOH + C3H7OH
d. C3H7 C O C3H7
13. b. C15H31COONa + C4H9OH
O

f. C2H5 C O C2H5 14. c. HCOO — CH2 — C6H5

f. C3H7COOC3H7 + H2O
O CH3

h. H C O C CH3 15. b. O O
CH3 CH3 C Cl + (CH3)3COH CH3 C O C(CH3)3 + HCl
Cl O

j. H C C O CH3

Cl 16. CH3COOC3H7
O
17. II. CH3COOC2H5, 78 g/mol
l. C2H3 C O CH3

O CH3 18. 118 g/mol

n. H C O CH2 C CH3 23. 40 g

CH3
25. 2.76 g
O

p. H C O C2H5 27. a. C3H5(C17H33COO)3 + 3NaOH o 3C17H33COONa + C3H5(OH)3

OH 30. a. V, b. III, c. VI, d. I, e. II, f. IV

O

s. CH3 CH C O

CH3

Oxygen And Nitrogen Containing Organic Compounds 249

 Chapter_5 CARBOHYDRATES Chapter_6 AMINES, AMIDES AND AMINO ACIDS
11. b. H C O c. CH2 O 2. b. trimethyl amine, tertiary
H C OH C O
d. methyl cyclopentyl amine, secondary

H C OH H C OH
3. b. CH3 N CH3
CH2 OH H C OH
C2H5
H C OH
d. CH3 N C 2 H5
CH2 OH
CH3 CH CH3

22. H C O
4. 16.5%
(H C OH)4

CH2OH 5. NH2 C2H5

23. 14.3 g
7. 4 . 10–4
24. 43.2 g

25. 90% 8. sec – amine (CH3)2NH

10. b. N – methyl – N – ethyl acetamide
26. a. C6H12O6
d. butryramide (butanamide)
b. 180 g/mol

11. 20.65 g

12. 17.4 g

15. 7.76 g

18. 1482 g/mol

19. 99

250 Oxygen And Nitrogen Containing Organic Compounds

 Chapter_7 AROMATIC COMPOUNDS
1. CH3 19. 50% 34. b. O
b.
NO2 C Cl
22. b. OH

d.
e. CH3
CH3
NO2
OH O
f.
NO2 H C C H
OH
Cl Br
OH O
2. a. o – methyl nitro benzene f.
C CH3
d. 4 – bromo – m – dinitro chloro
23. a. dihydroxybenzene
benzyl
c. m – methyl – p – nitrophenol

8. 227 g/mol 25. III > II > I > IV

37. 21.2 g
10. para > meta > ortho 27. a. Benzyl alcohol
b. Phenyl ethanol
39. b. COOH
12. c. m – hydroxy benzyl alcohol
b. N COOH
d. 2 – phenyl – 2 – propanol
H
28. OH CH3
c.
+
NH3 Br
– c.
C CH
c. COOH

H CH3
e. CH3
d. CH2OH

COOH

CCl3 40. c. 3 – hydroxy – 5 – methylbenzoic

NH2 acid
d. 3 – chloro – m – phthalic acid
13. a. o – methyl aniline 30. C6H5 CH2 OH
c. m – tert – butyl aniline 41. II > I > III
33. b. o – methylbenzaldehyde
d. 2 – amino – 2 – chloro
14. III > II > IV > I benzaldehyde 45. a. 24.53 g
b. 665 mL
15. c. trinitro toluene
46. X : C6H5CH2OH
18. a. 0.3 mol Y : H2O
b. 67.2 g
Z : HCl
c. 7200 ml

Oxygen And Nitrogen Containing Organic Compounds 251

 MULTIPLE C HOICE

Chapter_1 ALCOHOLS AND ETHERS Chapter_5 CARBOHYDRATES

1. D 6. A 11. B 16. D 21. A 1. C 5. D 8. E 11. E 14. A

2. E 7. A 12. D 17. A 22. A 2. D 6. B 9. A 12. E 15. A
3. A 8. C 13. B 18. A 23. C 3. E 7. E 10. D 13. C 16. B
4. A 9. C 14. B 19. C 24. E 4. D
5. E 10. B 15. B 20. B 25. E

Chapter_2 ALDEHYDES AND KETONES Chapter_6 AMINES, AMIDES AND AMINO ACIDS

1. B 7. C 13. B 19. E 25. C 1. E 4. B 7. A 10. D 13. E

2. A 8. A 14. C 20. A 26. E 2. C 5. D 8. E 11. D 14. A
3. A 9. A 15. B 21. D 27. D 3. C 6. C 9. D 12. B 15. E
4. B 10. B 16. C 22. B
5. C 11. A 17. E 23. E
6. E 12. C 18. B 24. B

Chapter_3 CARBOXYLIC ACIDS Chapter_7 AROMATIC COMPOUNDS

1. D 8. E 15. B 22. C 29. A 1. E 10. B 19. A 28. A 37. B

2. C 9. E 16. B 23. B 30. E 2. A 11. C 20. D 29. E 38. C
3. B 10. B 17. A 24. E 3. D 12. A 21. D 30. E 39. B
4. B 11. C 18. C 25. C 4. D 13. D 22. C 31. E
5. B 12. A 19. E 26. E 5. E 14. E 23. A 32. E
6. D 13. C 20. A 27. E 6. B 15. C 24. B 33. E
7. B 14. E 21. B 28. C 7. E 16. A 25. D 34. C
8. B 17. D 26. C 35. D
9. C 18. C 27. C 36. E

Chapter_4 ESTERS

1. B 4. A 7. D 10. B 13. A
2. E 5. D 8. C 11. C 14. C
3. E 6. E 9. B 12. E

252 Oxygen And Nitrogen Containing Organic Compounds

 PUZZLE

Chapter_1 ALCOHOLS AND ETHERS Chapter_3 CARBOXYLIC ACIDS

S O LV E A N D F I T P U Z Z L E DOUBLE PUZZLE

M E T H A N O L 1 C A R B O 7X Y L I C A C I D S
P G T L
O L E C G 21 11
L M O N O H Y D R I C A L C O H O L S
2 C A R B O X Y L I C A C I D S
Y C T H Y
13
H E I O C 3 C A R B O X Y L G R O U P
Y P R I M A R Y A L C O H O L S O
D I R S L 3
4 P R O P A N O I C A C I D
R G N Y
I N C R E A S E A L D E H Y D E S E
8
C I L T 5 H Y D R O X Y A C I D
A G C H
16
L N K E T O N E S S I M P L E 6 A M I N O A C I D S
C A H R
O R C A R B O X Y L I C A C I D S 9
7 F O R M I C A C I D
H D L
O S
4
L 8 A C E T I C A C I D
S
18
9 O X A L I C A C I D

5
Chapter_2 ALDEHYDES AND KETONES 10 C I T R I C A C I D

19
11 E S T E R S
DOUBLE PUZZLE
8
1 C A R B O N Y L

14
SECRET MESSAGE
2 A L D E H Y D E
9 16 8 21 13 7 11 18 3 9 16 9 3 5 19

2
C A R B O X Y L I C A C I D S
3 F O R M A L D E H Y D E
16 8 4 10 4 16 23 16 9 3 5 19
4 T O L L E N S R E
24
A G E N T A R E W E A K A C I D S

13 32
5 P R I M A R Y A L C O H O L S

6
6 A C E T A L D E H Y D E

11
7 K E T O N E S

8 I S O M E R
20
S
Chapter_4 ESTERS
10
9 K E T O N E S WORD SEARCH
23 9
10 S E C O N D A R Y A L C O H O L S

5
M Q E F S P R O S K S M R H X
11 A C E T O N E
R E H E A O S L V G Q A E H Q
12 F O R M A L
41
I N
O L T W D R A M H Q D I T C R
F U W H E I E P O P E A A T A
13 C A R B O X
7
Y L I C A C I D S F J T T Y H R Y T D P H W U S
12
P Z S Z C L A E L W Y T D N M
14 S I M P L E
E E M S I O F U C D A D R S I
19
15 P R O P A N O N E L K F P G H W O R Y X R A A C
K Q R T R P V O R J L R H T A
F A T S P M P Q V M B G C U X
SECRET MESSAGE X D M D J H P R V P A F D R C
6 9
T H E R E
17 24 17 41
A R E
24 17 6 4
T W O
11 6
T Y P
13 19 17
E
32
S
11
O F
2 H T V B O F S B K J X T V A I
5 41 24 7 11 8 13 14 5 11 20 19 11 39 8 23 32
G P Z B P N R I C T G D E T G
C A R B O N Y L C O M P O U N D S
41 14 23 17 9 13 23 17 32 41 8 23 10 17 6 11 8 17 32
N I I S E N I R A G R A M E W
A L D E H Y D E S A N D K E T O N E S E C T Z A O I L L F V R S D S

Oxygen And Nitrogen Containing Organic Compounds 253

Chapter_5 CARBOHYDRATES Chapter_7 AROMATIC COMPOUNDS

CRISS – CROSS PUZZLE CRISS – CROSS PUZZLE

1 2 3
P C K 1 2
4
C B
P H O T O S Y N T H E S I S E 3
A A N A L I N E
L L T 4
R T K
Y L O 5
S U S
B E N Z A L D E H Y D E
5
S T A R C H
6
G L U C O S E O T L
6
C O X I N D I G O
7 8
C F R U C T O S E A Y T
7
H E L L P H E N O L S
A D I E
9
C A R B O H Y D R A T E O
C T
I S
10
D I S A C C H A R I D E
E

Chapter_6 AMINES, AMIDES AND AMINO ACIDS

CRISS – CROSS PUZZLE

1 2 3
A A M I N O A C I D S
C M M
4
E I P E P T I D E
T D H
5
A M I D E S O
6
M S P R O T E I N S
I E
D R
7
E P R I M A R Y
C

254 Oxygen And Nitrogen Containing Organic Compounds


acetal, 75
acetaldehyde, 83
acetate ion, 116
acetic acid (see ethanoic acid)
acetamide, 206
acetone, 97
acetophenone, 87
acetyl chloride, 210
acetylene, 129
acid halide, 155
acrylic acid, 113, 130
acrylonitrile, 131
acyl group, 119, 158
adipic acid, 132, 134
alcohol, 10 – 47, 75, 81
aldehyde, 64 – 84
aldose, 177, 182
aldotetrose, 177
aldotriose, 177
aliphatic, 71, 108, 223
aliphatic aldehyde, 64, 225
alkanamides, 115
alkanoates, 155
alkenes, 36, 124
alkoxide, 22, 75 – 76
amides, 204 – 206
amines, 198 – 204
amino acid, 109, 198, 207 – 209
ammonia, 69, 82
aniline, 202, 221 – 222
aromatic, 223, 225, 226
asymmetric carbon, 140
Baekeland, L.H, 222
bakelite, 218
Baeyer, A., 218, 221
benzaldehyde, 68, 225 – 226
benzoic acid, 113, 227
benzonitriles, 228
benzophenone, 87
benzyl alcohol, 223
benzyl phenyl ketone, 85
Butlerov, A., 81
butyl alcohol, 20
butyraldehyde, 68
butyric acid, 109, 113
INDEX
calcium acetate, 97 ethyl chloride, 37
calcium carbide, 44 ethyl isopropyl ether, 49
Cannizaro reaction, 82 ethyl methyl ether, 48
carbohydrate, 176 – 178 ethyl methyl ketone, 85
carbon dioxide, 40, 126, 133 ethylene, 31
carbonic acid, 126, 137 ethylene glycol (see glycol),
carboxyl group, 108 – 112, 119, 135, 198 fat, 164 – 167
carboxylate, 116, 124, 125 fatty acid, 162, 166
carboxylate salts, 116, 125 Fehling’s reagent, 71, 72, 180
carboxylic acid, 25, 26, 96, 109, 112, 161 fermentation method, 42, 43, 47
carboxylic acid salt, 217 formaldehyde, 64, 65, 81 – 83
carcinogen, 84, 219 formalin, 81, 82
cellobiose, 186, 188 formate ion, 113
cellulose, 188, 190 formic acid, 108 – 114, 125 – 128
cellulose trinitrate, 190 fructose, 178, 181, 186
chiral molecule, 138, 139 galactose, 178, 187
chlorobenzene, 216 glucose, 43, 178 – 190
chlorophyll, 176 glycerine, 47, 162 – 165
citric acid, 137 glycerol (see glycerine),
combustion reaction, 35, 78, 95 glycogen, 188, 189
cresol, 216, 223 glycol, 45
cyanohydrine, 76 Grignard reagent, 38, 39, 76, 92
dacron, 228 hemiacetal, 75, 179
dehydration, 29, 53, 208 hemiketal, 89
dehydrogenation, 81, 83, 96 hemoglobin, 219
detergent, 169 hydrocarbon, 15 – 18, 67, 74
dextrine, 189 hydrolysis, 47, 124 – 125, 158, 165, 188, 189
diethyl ether, 54, 201 hydroxy acid, 109, 122, 137
dimethyl ketone, 97 indigo, 221
dinitrobenzene, 220 isopenthyl acetate, 156, 157
disaccharide, 186, 187 isopropyl alcohol, 20, 97
disinfectant, 42, 48, 82, 128 keto acids, 109
D–Ribose, 177 ketone, 85 – 91
electrophile, 27, 219 ketopentose, 178, 185
enantiomers, 138 – 139 ketotetrose, 178
esterification, 25, 120, 154, 160 lactic acid, 136 – 138
esters, 154 – 162 lactose, 186, 187
ethanal, 68, 69, 71 linoleic acid, 135
ethanol (see ethyl alcohol), linolenic acid, 135
ethanoic acid, 113, 128 – 130 lithium aluminum hydride, 74
ethers, 47 – 54 Lucas reagent, 28, 29
ethyl acetate, 156, 157 malic acid, 133, 137
ethyl alcohol, 41, 43 malonic acid, 133
ethyl benzoate, 157 maltose, 186 – 189
ethyl butanoate, 157 mannose, 178
Oxygen And Nitrogen Containing Organic Compounds 255
Markovnikov’s rule, 29, 36 parapolymerization, 78 silver mirror, 69
m-dinitrobenzene, 220 peptide, 208, 209 simple ketone, 85
methanal (see formaldehyde) phenol, 11, 216 – 218 sodium bisulfite, 93
methanoic acid (see formic acid) phenol formaldehyde (see bakelite) sodium borohydride, 74
methanol (see methyl alcohol) phenylamine (see aniline) sodium hydroxide, 37, 117
methoxymethane, 50 phenylethyl amine, 200 sorbitol, 184
methylalcohol, 12, 39 – 41, 83 photosynthesis, 176 starch, 187 – 189
methyl phenyl ether, 48 phthalic acid, 226 stearic acid, 135, 163
methyl tertiary butyl ketone, 85 polyethylene terephthalate, 228 succinic acid, 132
monocarboxylic acid, 108, 112, 124 polyhydric alcohol, 12, 47 sucrose, 176, 186 – 187
monohydric alcohol, 12, 26, 35 polymer, 82, 83 tartaric acid, 137
monosaccharide, 178 – 180, 188 polymerization, 68, 78, 84, 218 terephthalic acid, 228
neutralization reactions, 117, 128, 154 polysaccharide, 178, 181, 188 – 190 tertiary alcohol, 13 – 14, 29, 38
nitration, 219, 220 potassium permanganate, 47, 72 tetrahydrofurane, 48
nitrobenzene, 219, 220 primary alcohol, 12, 13, 38, 39, 158 Tollens' reagent, 69 – 71
nitrocellulose, 157 propanal, 68, 72 toluene, 220, 225
n–propanol, 13, 15, 22, 29, 33 propanone (see acetone) trinitrotoluene, 220
Nobel, A.B, 45 propenyl alcohol, 14 trinitrobenzene, 218
oleic acid, 135 propionaldehyde (see propanal) trinitroglycerine, 47
optical isomerism, 138 propionic acid, 108, 110, 113 urea, 207
oxalic acid, 45, 132, 133 protein, 208, 209 urine, 97, 183
oxidation, 31 – 35, 68, 69, 79 – 83, 95, 97, p–xylene, 228 urotropine, 82
123, 124, 133, 180, 233 pyrogallol, 216 valeraldehyde, 66, 68
oxy acid, 136, 137 reduction, 37, 81, 88, 122, 158, 184, 221 Williamson synthesis of ethers, 54
palmitic acid, 135 saccharose (see sucrose) Wöhler, F., 207
paraldehyde, 84 salicylic acid, 113, 150 Zwitterion, 208
paraformaldehyde, 83 saponification, 158, 165
paraphthalic acid, 228 secondary alcohol, 13, 14, 38

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256 Oxygen And Nitrogen Containing Organic Compounds