Chimistry Senior 5 BCM Final

CHEMISTRY COURSE FOR S5MCB&PCM&PCB
Table of content
PREFACE ................................................................................................................... 1
Acknowledgments .......................................................................................................... 2
CHAP 0: Introduction...................................................................................................... 3
0.1 Application of organic chemistry ......................................................................................................................... 4
0.2.General objectives: ............................................................................................................................................... 4
CHAP I: GENERAL INTRODUCTION TO ORGANIC CHEMISTRY

CONCEPTS ............................................................................................................ 5
I.1 Carbon background .......................................................................................................................... 5
I.2. Functional groups .......................................................................................................................... 6
I.3. Empirical, Molecular and structural formulae ................................................................................. 7
I.3.1.Empirical formula ..................................................................................................................... 7
I.3. 2. Molecular formula ................................................................................................................... 8
I.3.3. Structural formula................................................................................................................... 10
I.4. Inductive effect ............................................................................................................................. 12
CHAP II: ALKANES ............................................................................................ 14

I.1 Introduction and definition ............................................................................................................. 14
I.2 Nomenclature and isomerism ......................................................................................................... 14
II.3 PHYSICAL AND CHEMICAL PROPERTIES ............................................................................. 18
II.3.1 Physical properties ................................................................................................................. 18
II.3.2. CHEMICAL PROPERTIES .................................................................................................. 20
II.4. GENERAL METHODS OF PREPARATIONS OF ALKANES ................................................... 21
II.5. USES ........................................................................................................................................... 22
II.6.EXERCISES................................................................................................................................. 22
CHAP III: ALKENES .......................................................................................... 24

III.1 Definition and introduction .......................................................................................................... 24
III.2 Nomenclature and isomerism ...................................................................................................... 24
III.3 PHYSICAL AND CHEMICAL PROPERTIES ........................................................................... 26
III.3.1 Physical properties ................................................................................................................ 26
III.3.2 CHEMICAL PROPERTIES .................................................................................................. 26
III.4 General methods of Preparations.................................................................................................. 34
III.5 USES .......................................................................................................................................... 35
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III.6 EXERCISES ............................................................................................................................... 36
CHAP IV: ALKYNES ........................................................................................... 37

IV.1. Introduction................................................................................................................................ 37
IV.2 Nomenclature and isomerism....................................................................................................... 37
IV.3 PHYSICAL AND CHEMICAL PROPERTIES ........................................................................... 38
IV.3.1 Physical properties ................................................................................................................ 38
IV.3.2 Chemical properties .............................................................................................................. 38
IV.4 General methods of preparation ................................................................................................... 40
IV.5 USES .......................................................................................................................................... 41
IV.6 EXERCISES ............................................................................................................................... 41
CHAP V: PETROLEUM AND ITS ENGINEERING CHEMISTRY.................. 43

V.1 Introduction .................................................................................................................................. 43
V.1.1 Petroleum origin and formation .............................................................................................. 43
V.1.2. Petroleum engineering and petroleum treatment .................................................................... 44
V.2. Refining of petroleum .................................................................................................................. 45
V.2.1 Purification ............................................................................................................................ 46
V.2.2 Cracking ................................................................................................................................ 46
V.2.3. Reforming............................................................................................................................. 48
V. 3. USES of petrol............................................................................................................................ 48
V.4 Exercises ...................................................................................................................................... 49
CHAP VI: ALKYL HALIDES .............................................................................. 51

VI.1.Definition and introduction .......................................................................................................... 51
VI.2. Nomenclature and isomerism...................................................................................................... 51
VI.3.Physical and chemical properties ................................................................................................. 52
VI.3.1 Physical properties ................................................................................................................ 52
VI.2.2Chemical properties ............................................................................................................... 52
V.4 Preparation of alkyl halides........................................................................................................... 55
VI.5 Alkyl halides uses ....................................................................................................................... 56
VI.6. EXERCISES .............................................................................................................................. 57
INDEX NOTE ...................................................................................................... 59

Isomerism ............................................................................................................. 59
CHAPVII: ALCOHOLS ....................................................................................... 63
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VII.1 Introduction ............................................................................................................................... 63

VII.2 Nomenclature and isomers ......................................................................................................... 63
VII.3 Physical and chemical properties ................................................................................................ 64
VII.3.1Physical properties ............................................................................................................... 64
VII.3.2 CHEMCAL PROPERTIES ................................................................................................. 65
VII. 4. Alcohol preparations ................................................................................................................ 69
VII.5. USES OF ALCOHOLS ............................................................................................................. 75
VII.6.EXERCICES ............................................................................................................................. 77
CHAP VIII: ETHERS .......................................................................................... 81

VIII.1 Introduction .............................................................................................................................. 81
VIII2. Nomenclature and isomerism .................................................................................................... 81
VIII.3. PHYSICAL AND CHEMICAL PROPERTIES ........................................................................ 82
VIII.3.1 Physical properties ............................................................................................................. 82
VIII. 3.2 Chemical properties .......................................................................................................... 82
VIII.4. General methods of preparation................................................................................................ 83
VIII.5. USES....................................................................................................................................... 83
VIII.6 EXERCICES ............................................................................................................................ 84
CHAP IX: AMINES ............................................................................................. 86

IX.1 Introduction and definition .......................................................................................................... 86
IX.2 Nomenclature and isomerism....................................................................................................... 86
IX.3 Physical and chemical properties of amines ................................................................................. 87
IX.3.1 Physical properties ................................................................................................................... 87
IX. 3.2 Chemical properties ............................................................................................................. 88
IX.4 Preparation of amines .................................................................................................................. 91
IX.5 Uses ............................................................................................................................................ 92
IX.6 EXERCICES............................................................................................................................... 93
CHAP X: CARBONYL COMPOUNDS: ALDEHYDES AND KETONES .......... 95

X.1 Introduction and definitions .......................................................................................................... 95
X.2. Nomenclature and isomerism ....................................................................................................... 95
X.3. Physical properties and chemical properties ................................................................................. 97
X.3.1 Physical properties ................................................................................................................. 97
X.3.2 CHEMICAL PROPERTIES ................................................................................................... 97
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X. 4. ALDEHYDES AND KETONES PREPARATIONS ................................................................. 105

X.6 EXERCICES .............................................................................................................................. 108
CHAP XI: CARBOXYLIC ACIDS ..................................................................... 112

XI.1 Introduction and definition ........................................................................................................ 112
XI.2 Nomenclature and isomerism..................................................................................................... 112
XI 3.Physical and chemical properties ........................................................................................... 114
XI.3.1 Physical properties .............................................................................................................. 114
XI. 3.2 CHEMICAL PROPERTIES .............................................................................................. 114
XI.4 Methods of preparation of carboxylic acids................................................................................ 120
XI 5.Uses .......................................................................................................................................... 121
XI.6 EXERCICES............................................................................................................................. 122
CHAP XII: FUNCTIONAL DERIVATIVES OF CARBOXYLIC ACIDS ........ 124

XII.1 Introduction and definition ....................................................................................................... 124
ACID CHLORIDES ........................................................................................... 125

A.1.1 Physical properties ............................................................................................................... 125
A.1.2 Chemical properties ............................................................................................................. 125
A.2.Preparation methods ................................................................................................................... 126
A.3 Uses ........................................................................................................................................... 127
B.ESTERS .......................................................................................................... 127

B.1 Definition: .................................................................................................................................. 127
B.2 Nomenclature and isomerism ...................................................................................................... 127
B.3 Physical and chemical properties................................................................................................. 127
B.3.1 Physical properties ............................................................................................................... 127
B. 4.Esters preparation ...................................................................................................................... 128
B.5 USES.......................................................................................................................................... 129
C.AMIDES.......................................................................................................... 129
C.1 Definition ................................................................................................................................... 130
C.2. Nomenclature and isomerism ..................................................................................................... 130
C.3 Physical and chemical properties................................................................................................. 130
1.1 Physical properties. ............................................................................................................ 131
C.3.2 Chemical properties ............................................................................................................. 131
C. 4. Preparation of amides................................................................................................................ 132
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C.5 Uses............................................................................................................................................ 133
D.ACID ANHYDRIDES ..................................................................................... 134

1.Definitions and introductions .......................................................................................................... 134
2.Nomenclature and isomers.............................................................................................................. 134
3.Physical and chemical properties ................................................................................................... 135
3.1 Physical properties ............................................................................................................. 135
3.2 Chemical properties ................................................................................................................. 135
4. Preparations of acid anhydrides ................................................................................................ 136
5. Uses .............................................................................................................................................. 136
E .NITRILES ...................................................................................................... 137

1.Definition ........................................................................................... Error! Bookmark not defined.
2.Nomenclature and isomerism.......................................................................................................... 137
E.3 Physical and chemical properties ................................................................................................. 138
3.1 Physical properties................................................................................................................... 138
3.2.Chemical properties ................................................................................................................. 138
E.4 Preparations of nitriles ................................................................................................................ 139
E.5 Uses ............................................................................................................................................ 139
EXERCISES ....................................................................................................... 140

CHAP XIII: LIPIDS........................................................................................... 145
XIII.1 Introduction ............................................................................................................................ 145
XIII.2.Nomenclature classification and physical properties ................................................................ 145
XIII.3 Physical and chemical properties............................................................................................. 148
XIII.3.1 Physical properties ........................................................................................................... 148
XIII. 3.2. Chemical properties........................................................................................................ 148
XIII.4 Uses of lipids .......................................................................................................................... 149
REVIEW QUESTIONS ON LIPIDS.................................................................. 150
CHAP XIV: CARBOHYDRATES ...................................................................... 151

XIV.1 Introduction and definition...................................................................................................... 151
XIV.2 Nomenclature and isomerism .................................................................................................. 151
XIV.3 Physical and chemical properties ............................................................................................ 157
XIV.3.1 Physical properties ........................................................................................................... 157
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XIV.3.2 Chemical properties ......................................................................................................... 157

XIV.4. Carbohydrate preparations ..................................................................................................... 162
XIV.5 USES ..................................................................................................................................... 162
XIV.6.Exercises ................................................................................................................................ 163
CHAP XV: AMINO ACIDS AND PROTEINS .................................................. 164

XV.1 Introduction and definition ....................................................................................................... 164
XV.2 Nomenclature and isomerism ................................................................................................... 164
XV.3 Physical and chemical properties............................................................................................. 167
XV.3.1Physical properties ............................................................................................................. 167
XV.3.2 Chemical properties .......................................................................................................... 167
XV.4 Preparation of amino acids ....................................................................................................... 172
XV.5 Uses of amino acids. ................................................................................................................ 173
REFERENCES................................................................................................... 174
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PREFACE
Students come to an organic chemistry course in senior five (Advanced level) with a variety of
background and interest according to their combinations but, most of them plan to become
scientists, engineers, or professionals in chemistry and other related fields such as medicine and
pharmacy more generally including areas of life science.
Part of the task of the chemistry facilitator in advanced level(senior five of all chemistry
combinations that deal with chemistry) is to convince students that knowledge of chemistry is
essential to a true understanding of field that range from cell biology to medicine and material
science.
Indeed, the chemical properties and principles students will learn in this course will pervade
almost every aspect of their personal and professional lives. In this text, we have tried to provide
students with both the core principles and interesting applications of organic chemistry with the
belief that such knowledge will both help them in their professions and enrich their everyday life.
In addition to establishing the relevance of organic chemistry to broader concerns, a textbook can
enhance students’ success in the study of chemistry by satisfying other needs: the need for
background reading and a second voice for students to hear, help in visualizing chemical
phenomena, both what students can see with their eyes and what they must learn to observe with
their minds’ eyes ; and help in formulating strategies for solving problems, the basis on which
their knowledge will so often be tested.
Through the different types of examples, exercises described, learners of this designed course
should gain a balanced set of skills in chemical problem –solving and the ability to think
critically(which are essential for success in today’s world); and with additional reinforcement,
the text offers three kinds of end-of-chapter exercises:
• Activities that are arranged by topics in subtopics in order to assess knowledge in

continuous test procedure but as self-assessment while others are with control and be
marked. This will help the facilitator to supervise learners and make follow up and
encourage them to improve.
• Review questions are intended to provide a qualitative measure of student understanding
of the main ideas introduced in the chapter. Answers to a few of the review questions are
given as closed to the question. Indeed, it is a task to the facilitator and learners to solve
others.
• Exercises assigned at the end of each chapter will be solved after going through the text
and of course mastering the content. So, it is a task to the facilitator and learners that use
this book as a guide to find out reasonable answers to provided questions. But for some,
answers are provided and we guarantee you that they are total correct since they were
revised with specialist in content several times.
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Acknowledgments
I, Mr. NKURANGA Jean Bosco, chemistry facilitator at Junior seminar Saint Léon of
KABGAYI, would like to express my gratitude and sincere thanks to the father Rector of Junior
Seminar Saint Léon of KABGAYI, Celse in particular, father deputy in charge of academic issue,
T.Télésphore, Sister Headmistress of E.S.KIRUHURA, U. Immaculée, Headmaster of G.S.
SHYOGWE, N.Paul, colleagues and all of who played an instrumental part in completion of this
book.
But, I keep special note to Mr. H. RUDAKEMWA, D. HARELIMANA closed colleagues to their
guidance and constructive ideas plus discussion and harmonization we did, words of wisdom and
ever present tendency to help certainly have been invaluable all though during the reduction
period. I sincerely thank Prof. Dr. R.RULINDA Jean Baptiste, Lecturer at National University of
RWANDA for his reading and molding me; and consequently enabling me to be ready for his
editing oriented career, Prof. Dr. Lewis, Lecturer of organic chemistry at Fondation Universitaire
Luxembourgeoise for his correspondence education.
I would also like to acknowledge the entire chemistry department Lecturer’s who help me to get
on overall knowledge about the field, which is imperative in doing publication dealing with
academic relevant. I would like to mention a special note of thanks to the Director of NUR main
library, Mr. KARINGANIRE Charles for documentation access and his guidance and encourage
me to work hard.
I would like to finish by thanking my parents who are responsible for my being in this position in
the first place. Their patience, confidence and advice have been invaluable all through my life.
 

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CHAP 0: Introduction
At the very beginning of the nineteenth century chemists generally thought that compounds from living organisms
were too complicated in structure to be artificially synthesized from non-living things, and that a 'vital force' or
vitalism conferred the characteristics of living beings on this form of matter. They named these compounds 'organic',
and preferred to direct their investigations toward inorganic materials that seemed more promising but few.
Organic chemistry received a boost when it was realized that these compounds could be treated in ways similar to
inorganic compounds and could be created in the laboratory by means other than 'vital force'. Around 1816 Michel
Chevreul started a study of soaps made from various fats and alkali. He separated the different acids that, in
combination with the alkali, produced the soap. Since these were all individual compounds, he demonstrated that it
was possible to make a chemical change in various fats (which traditionally come from organic sources), producing
new compounds, without 'vital force'.
In 1828 Friedrich Wöhler first manufactured the organic chemical urea (carbamide), a constituent of urine, from the
inorganic ammonium isocyanate NH4OCN by heating, in what is now called the Wöhler synthesis.
Although Wöhler was, at this time as well as afterwards, cautious about claiming that he had thereby destroyed the
theory of vital force, most have looked to this event as the turning point.
A great next step was when in 1856 William Henry Perkin, while trying to manufacture quinine, again accidentally
came to manufacture the organic dye now called Perkin's mauve, which by generating a huge amount of money
greatly increased interest in organic chemistry. Another step was the laboratory preparation of DDT by Othmer
Zeidler in 1874, but the insecticide properties of this compound were not discovered until much later. The crucial
breakthrough for the theory of organic chemistry was the concept of chemical structure, developed independently and
simultaneously by Friedrich August Kekule and Archibald Scott Couper in 1858.
Hence, Organic chemistry is a discipline within chemistry which involves the scientific study of the structure,
properties, composition, reactions, and preparation (by synthesis or by other means) of chemical compounds
consisting primarily of carbon and hydrogen, which may contain any number of other elements, including nitrogen,
oxygen, the halogens( chlorine, fluorine, bromine, iodine) and other chemical elements as well as phosphorus, silicon
and sulfur and further more metals like tin, Na, K, Lead, Ca, Cu, Zn, Li, Al, Hg, … .
The original definition of "organic" chemistry came from the misconception that organic compounds were always
related to life processes. However, organic molecules can be produced by processes not involving life. Life, as we
know, it also depends on inorganic chemistry that deals with inorganic compounds.
For example, many enzymes rely on transition metals such as iron and copper; and materials such as shells, teeth and
bones are part organic, part inorganic in composition. Apart from elemental carbon, only certain classes of carbon
compounds (such as oxides, carbonates, and carbides) are conventionally considered as inorganic.
But Biochemistry deals mainly with the natural chemistry of biomolecular components such as proteins
(hemoglobin, casein, …) , nucleic acids (DNA, RNA), and sugars (fructose, glucose, sucrose, starch,..), fats,
vitamins, enzymes ( biocatalyst) .
Organic compounds form the basis of , or are important constituents of many products (paints, plastics, food,
explosives, drugs, petrochemicals, pesticides, soaps and cosmetics like perfume, clothes, …) and (apart from a very
3
few exceptions) they form the basis of all earthly life processes and further we can say that “we live in the era of
organic chemistry”.
Current (as of 2008) trends in organic chemistry include chiral molecule synthesis, green chemistry, microwave
chemistry, fullerenes and microwave spectroscopy.
The following major properties that characterize organic compounds that can distinguish organic compounds from
inorganic compounds:
• Most organic compounds are liquid, others are gas and a few are solid.
• Lower density(less than 1.00 or closed to 1.00, the one of water) characterizes organic compounds.
• Organic compounds frequently exhibit isomerism while inorganic almost do not except complex molecules
(see the course of senior 4).
• Organic compounds are characterized by lower boiling and melting point within reference to inorganic
compounds since some are ionic compounds.
• Are usually insoluble in water but soluble in organic solvents like CCl4, CS2, benzene, ether, acetone, etc
• Organic compounds frequently have covalent bonding while inorganic can have ionic and or covalent
bonding reason they do not allow the electricity to pass easily compared to mineral compounds.
• Organic compounds have complex but slower reaction compared to inorganic compounds.
• Organic compounds are more volatile than inorganic, and can be easily broken down by the effect of heat
(lower thermal stability) reason why they can be used by source of energy ( fuels, oil for combustion).
0.1 Application of organic chemistry
Organic chemistry is applied in many field of our everyday life such as:
• Petroleum industry in refinery of petroleum oil and its treatment to get quality fuels, kerosene, mazout,
gasoline and other derivatives resulting from petroleum,….
• Pharmaceutical industry: drug synthesis and medicines, additives, antibiotics…
• Agriculture domain by synthesis of pesticides like DDT, herbicides, fungicides, …
• Plastic industry: polymer synthesis like rubber, polyethylene, PVC pipes …
• Paints, dyes, varnishes industry and solvents synthesis.
• Cosmetic synthesis like soaps, detergents, perfume, glycerin…
• Explosive synthesis like TNT: Trinitrotoluene (grenade powder), TNG: Trinitro glycerine (dynamite)…
0.2.General objectives:
Due to the fact that organic molecule are as many as possible, we can not memorize all possible structure
and chemical reactions in organic chemistry as it is in inorganic chemistry, but by the end of this part of
organic chemistry in senior five of all combinations that deal with chemistry (MCB, PCB and PCM), the
learners should be able to:
• Define and characterize each function group.
• Classify functional groups into sub-classes if exist,
• Give the correct nomenclature and isomers for any functional group
• Explain physical and chemical properties of any functional groups including chemical tests of
identification in qualitative laboratory analyses,
• Perform the preparation of any functional groups
• Suggest the use and desadvantages of any functional group.
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CHAP I: GENERAL INTRODUCTION TO ORGANIC CHEMISTRY CONCEPTS
I.1 Carbon background
The central atom in organic compounds is carbon with electronic configuration of 1s22s22p2 since Z=6. This
configuration therefore gives the valence of carbon as 2 but it shows a valence of 4 in all cases as discussed in senior
four. The valence of 4is due to sp3 hybridization where there is promotion of the 2s electrons to 2p sub-energy level
since their energy levels are sufficiently closed because they have the same principal quantum number (n=2).
Indeed, the carbon ground state electronic configuration 1s2 2s2 2p2 while his
Excited state can be drawn as follow 1s22s12p3
-1
Energy in KJ.mol
n
otio
prom
tro n
elec
sp3 hybridization
2s2 2s1
2px1 2py1 2pz
2px1 2py1 2pz1
energy
supply
2
1s
excited state
ground state
Figure 1: Carbon hybridization
Because of the presence of a 4 unpaired electrons in the excited state, carbon shows a valence of 4 and therefore
forms 4 covalent bonds.
H
H C H
e.g. H
Carbon atom is unique because of:

1. It can form single, double or triple bonds
2. Can form 4 covalent bonds.
Note: Within reference to the hybridization as discussed in senior four, particular in organic chemistry 3 types of
hybridizations are known such as:
• Sp3 hybridization: this hybridization occurs in saturated hydrocarbons (alkanes) or organic compounds
with single bonds.
• Sp2 hybridization: this hybridization occurs in unsaturated hydrocarbons (alkenes) or organic
compounds with double bonds(C=C).
• Sp hybridization: this hybridization occurs in unsaturated hydrocarbons (alkynes) or organic compounds
with triple bonds ( C C ).
Activity 1:Through electronic configuration and orbital theory, show how can you determine the hybridization
of carbon in the following molecule: C2H6, C2H2, CH3-CH=CH2.
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I.2. Functional groups
A functional group is an atom or group of atoms in a molecule which determines the characteristic properties of that
molecule.
Table 1: Table of some organic functional groups
Exclusively Carbon Functional Groups

Group Formula Class Name Specific Example IUPAC Name Common Name
C-C Alkane CnH2n+2 ---- -ane CH3-CH3 Ethane
Alkene H2C=CH2 Ethene Ethylene
Alkyne HC≡CH Ethyne Acetylene
Arene C6H6 Benzene Benzene
Functional Groups with Single Bonds to Heteroatoms

Group Formula Class Name Specific Example IUPAC Name Common Name
Halide H3C-I Iodomethane Methyl iodide
Alcohol CH3CH2OH Ethanol Ethyl alcohol
Ether CH3CH2OCH2CH3 Diethyl ether Ether
Amine H3C-NH2 Aminomethane Methylamine
Nitro Compound H3C-NO2 Nitromethane
Thiol H3C-SH Methanethiol Methyl mercaptan
Sulfide H3C-S-CH3 Dimethyl sulfide
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Functional Groups with Multiple Bonds to Heteroatoms

Specific
Group Formula Class Name IUPAC Name Common Name
Example
Nitrile H3C-CN Ethanenitrile Acetonitrile
Aldehyde H3CCHO Ethanal Acetaldehyde
Ketone H3CCOCH3 Propanone Acetone
Carboxylic Acid H3CCO2H Ethanoic Acid Acetic acid
Ester H3CCO2CH2CH3 Ethyl ethanoate Ethyl acetate
Acid Halide H3CCOCl Ethanoyl chloride Acetyl chloride
N,N- N,N-
Amide H3CCON(CH3)2
Dimethylethanamide Dimethylacetamide
Acid Anhydride (H3CCO)2O Ethanoic anhydride Acetic anhydride
I.3. Empirical, Molecular and structural formulae
I.3.1.Empirical formula
This is the simplest formula which expresses the ratio of number of atoms of elements present in a molecule.
Empirical formula is calculated from the percentage composition.
The steps are :
i. The percentage of each element is divided by its atomic weight.
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ii. The result in i. above is now then divided by the smallest one among them to give the atomic ratio.
iii. If the atomic ratio obtained in ii. is not a whole number, then they should be multiplied by a suitable common
factor to convert each of them ton whole numbers. Minor fractions are to be ignored.
Example: 1. A certain organic compound has 39.13% by mass carbon, 52.23% oxygen and the rest of hydrogen.
Calculate the empirical formula of the compound.
Answer:
Elements C H O
% composition 39.13 8.64 52.23
Relative Ratio of 39.13
12 = 3.26 8.64
1 = 8.64 52.23
16 = 3.26
atoms,molecules
Atomic ratio 3.26
3.26 =1 8.64
3.26 = 2.65 3.26
3.26 =1
Empirical formula 3 7.95=8 3
:C3H8O3
Note: 2.65 can not be corrected to 3 so we multiply those atomic ratios with 3 .
I.3. 2. Molecular formula
This is a formula expressing the true number of atoms of various elements present in a molecule .
molecular weight
Molecular formula = Empirical formula *n where n= Empirical weight
when n=1, then the molecular formula is the same as the empirical formulae
Example 2: An organic compound that contains 31.9% by mass carbon, 6.8% hydrogen and 18.51% nitrogen the rest
being oxygen has a vapour density of 37.5. Calculate the molecula formula of the compound.
Answer:
Elements C H O N
% composition 31.9 6.8 42.79 18.51
12 = 2.568 6.8
1 = 6.8 42.79
16 = 2.674 18.51
14 =1.322
atoms,molecules
Atomic ratio 2.658
1.322 = 2.01 = 2 6.8
1.322 = 5.14 = 5 6.674
1.322 =2.02=2 1.322
1.322 =1
Empirical formula : C2H5NO2
Vapour density =½molecular weight
molecula weight = 2*vapour density= 2*37.5= 75gr/mol
n=
molecular weight
Empirical weight = 75
75 =1
hence molecular formule=empirical formula= C2H5NO2
Example 3. 0.45g of organic acid on combustion gave 0.44g of carbon dioxide and 0.09g of water.If the molecula weight of
the acid is 90, deduce the molecular formula.
Answer:
• 45 * 100 = 26.66 %
* 00..44
12
Percentage of carbon in CO2 : 44
• 45 * 100 = 2.22 %
* 00..09
2
Percentage of hydrogen in H2 O: 18
• Percentage of oxygen = 100-26.66-2.22=71.12%
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Elements C H O
% composition 26.66 2.22 71.12
12 = 2.22 2.22
1 = 2.22 71.12
16 = 4.44
atoms,molecules
Atomic ratio 2.22
2.22 =1 2.22
2.22 =1 4.44
2.22 =2
Empirical formula CHO2
Molecular formula n= 90/45=2 C 2H 2O4 Acide oxalique
Note: From the above calculation, we can extend our generalized expression:
% of carbon in CO2 =
12 mco2
× × 100
44 msample
2 mH 2O
% of hydrogen in H2O = × × 100
18 msample
% of Oxygen = 100 − (% of H 2 + % of carbone)
Activity1: The laboratory analyses of an organic compounds A containing carbon, hydrogen, nitrogen and oxygen
provide the following information in terms of percentage 58.45% for C; 4.95% for H; 17% for N and the rest is the
one of oxygen.
(i) Determine its empirical formula
(ii) Deduce from (i) the molecular formula of A if its molar mass is 170g.mol-1.
Gaseous hydrocarbon
A gaseous hydrocarbon exploded in air by the reaction
y
C x H y + (x + )O2 → xCO 2 + 2y H 2 O
4
When this is cooled, contraction in volume occurs due to the condensation of water vapour to liquid. The resultant
volume after contraction is due to excess O2 and CO2. The volume of CO2 is determined by adding aqueous NaOH or
KOH, which absorbs all the CO2.
Example 4: 15cm3 of a gaseous hydrocarbon were exploded with 105cm3 of oxygen, after cooling; the residual gas
occupied 75cm3. On addition of caustic potash, there was a fall in volume to 30cm3. What is the molecular formula of
the hydrocarbon?
Answer
• Volume of hydrocarbon reacting: 15cm3

• The volume of 75cm3= volume of unreacted O2 and of CO2 produced
• Volume of O2 reacted = (105-30)cm3=75cm3
y
By the reaction C x H y + (x + )O2 → xCO 2 + 2y H 2 O
4
V CO2 = X*VCxHy
45= x*15 → x=3
y
V O2 = (x + ) VCxHy
4
9
y
75 = (x + ) *15
4
y
5 = (3 + )
4
y=8
The molecular formula is C3H8 (propane)
CH3CH2CH3
Note: In physical chemistry, it is also possible to determine the molecular weight or mass of any substance by
measuring the freezing point depression and boiling point elevation in the laboratory. This was the preoccupation of
the practitioner RAOULT which stipulate that the freezing point depression or boiling point elevation is directly
proportional to molality of the solute in a solution of 1kg.
msolute
∆T f = − K f ×η = − K f ⋅
Mm ⋅ M solvent
Hence
msolute
∆Tb = + Kb ×η = + Kb ⋅
Mm ⋅ M solvent
• Kf and Kb are physical proportionality constant provided in physical table also called cryoscopic and
ebullioscopic constants. For example for water are 1.80 and 0.512 respectively.
• M is the mass of the solvent expressed in kilogram while m is the mass of the solute in gram, and Mm is the
molecular mass in g.mol-1.
• Tf and Tb are freezing point and boiling point expressed in Kelvin.
Example: Sorbitol is a sweet substance found in fruits and berries and sometimes used as sugar substituents
diabetes patients. An aqueous solution containing 1.00g in 100.00 g of water is found to have freezing point of -
0.1020C.
(i) What is the molar mass of sorbitol
(ii) Elemental analysis indicates that sorbitol consists of 39.56% in carbon, 7.75% in Hydrogen and the rest is
oxygen by mass.
• Find its empirical formula
• From it deduce the molecular formula of sorbitol
Answer: (i) The molar mass is deduced from RAOULT’s law:

K f ⋅ msrbitol
Mm = −
M water ⋅ ∆T f
−1.86 K × mol −1 Kg × 1.00 g
Mm = − = 182 g .mol −1
0.100 Kg × (−0.102 K )
(ii)From the molar mass and provided percentage of each atom of sorbitol, it is easy to prove that the empirical
formula is C3H7O3
The molecular formula is C6H14O6
I.3.3. Structural formula
Structural formula shows how the different atoms in a molecule are bonded (i.e. linked).
From the basic organic chemistry in ordinary level, different formulae have been discussed as well as empirical
formula, molecular formula, condensed formula, structural formula and further stick formula.
Table2: Table of different formulae used in organic chemistry molecular presentation
10
Molecular Condensed structural Structural formula Stick formula

formula
C 2H6 CH3CH3 H H
H C C H
H H
C4H8 CH3-CH2-CH=CH2 H H
H
H C C C C
H
H H H
Note: From the molar formula it is possible to suggest different possible structure, by calculating the deficiency index
i for any organic compound whose general formula is CnHmNzOy which allow us to know whether double or triple
bonds; or a ring are possible.
 z−m
i = n +1+   , with
 2 
n representing all tetravalent atoms,m for all monovalent atom,
z for all trivalent atoms like N and finall y for divalent atoms.
Note: If i=0 means that there is no double or triple bonds and even the ring.
Example: C3H6O has the deficiency number which is 1, therefore represent structure with one double bond let C=C,
C=O and a ring or cyclic compounds.
O
O
CH3 – CH2 – C
CH3 – O – CH = CH2 CH3 – C – CH3
H
H2C O
O CH2
OH
H2C CH
CH
H2C O CH3
CH2 HO-CH2-CH=CH2
cyclic
Alcohol ether Prop-2-en-1-ol
By contrast C2H6O has deficiency number which is zero, hence there is no double, triple bond and a ring. Hence, we
can suggest CH3-CH2OH and CH3-O-CH3.
From the above observation, we conclude that for one molecular formula, it is possible to obtain different structures
i.e. molecules. These structures are called isomers.
11
Briefly, isomers are organic compounds with same molecular formula but different structural formulae.
Activity 1: Give all possible structure whose molecular formula:

• C4H10 , C2H4, C3H6, C2H2, C2H4O2, C3H9N, C4H9Cl and C3H8O.
• Classify them in their respect function groups.
I.4. Inductive effect
This is the tendency of an atom or group of atoms to either pull electrons toward itself or push electrons away.
Inductive is characterized as positive (I+) (push electrons away) or negative (I-) (pull electrons towards themselves).
This can explain the origin of polarity in organic compounds which is the main causes of solubility of a given organic
compounds in a given solvent since like dissolves like and unlike dissolve unlike but like and unlike or vice-verse do
not.
Donors groups (like –OH, -NH2, -OCH3, -CH3 or alkyl in general) increase electron density therefore increase the
basicity while attractive groups (like –NO2, -COOH, -CHO, -CN and most electronegative atoms as well as fluorine,
chlorine, …) push electrons away and decrease electron density, therefore make it easiest hydrogen acid or protons
liberation or free (it is most available in solution), and consequently increase acidity.
Cl − CH 2 − CH 2 − CH 3
←     Li−CH 2 −
2CH CH 2 −CH 3
 →
Example: For example, chloroethanoic acid is a stronger acid than ethanoic acid. This is because chlorine being
electronegative, will withdraw electron towards itself thus reducing the electron density around the O-H bond thus
weakening. Hence O-H is easily broken and concentration of hydrogen ion will be the high in solution. Closely, the
more number of such groups, the greater is the effect and hence the more acidic will be the solution reason why
trifluoro acetic acid (CF3-COOH) is more acid than trichloro acetic (CCl3-COOH), dichloroacetic (Cl2CH-COOH),
chloro acetic (CH2Cl-COOH) and acetic acid (CH3-COOH) because fluorine which is more electronegative than
chlorine and hydrogen will strongly withdraw electron towards itself, hence make it easier the proton leaving.
O
Cl CH2 C O H
The direction of negative inductive effect:-I

Note: The further away the electronegative element, the less the effect for example 3-chloro butanoic acid (CH3-
CHCl-CH2-COOH) is therefore a weaker acid than 2-chlorobutanoic acid (CH3-CH2-CHCl-COOH).
Therefore, the strength of the base will depend on the availability of the non-bonded electron pair:
• For example, methylamine CH3-NH2 is therefore a stronger base than ammonia because of the presence of
the methyl group which has a positive inductive (electron pushing).
The methyl group pushes electrons towards the nitrogen atom and this increases the electron density on the nitrogen;
the non-bonded electrons are therefore easily available for proton attraction.
Aminobenzene or phenylamine or aniline C6H5-NH2 is weaker base than aliphatic primary amines because the non-
bonded pairs of electrons on the nitrogen atom become involved with the delocalization in the benzene ring
(resonance: is a term used to describe a situation in which several plausible Lewis structures can be written to
represent a species but in which a true structure can not be written. ) and hence is less available for proton attractions
this can be explain by electron withdraw from N to benzene ring as follow:
12
NH2 + NH2 + NH2 + NH2
- -
When the organic compounds contain conjugated double bonds i.e. alternating double, they can undergo resonance
which is the electron delocalization in a given molecule due inductive effect. The plausible structures are called
contributing structures or resonance structures and the true structure, which is a composite of contributing structures
is called resonance hybrid.
H H H
C C CH2- C
H2 C CH2 + CH2
C H2C C H2 C
H H C
H
resonance hybrid
O H +O H +O H +O H
- -
δ+ O H
δ− δ−
δ−
δ-
O O O O- O O- O O- O
N
O
N N N N
+
+ + δ δ+
+ δ+
Explain the acidity strength order of CH3-COOH and O2N-CH2-COOH.

Activity 1
(i) Explain briefly why CH3-NH2 is a stronger base than ClCH2-NH2
(ii) Aniline is less base than ethylamine CH3CH2-NH2

(iii) Trifluoro acetic acid (CF3-COOH) is more acid than trichloro acetic acid(CCl3COOH) and
acetic acid(CH3COOH).
13
CHAP II: ALKANES
I.1 Introduction and definition
Alkanes are saturated open chain hydrocarbons (formed by carbon and hydrogen atoms) with a general
formula CnH2n+2, they are saturated because all 4 valences of carbon are all satisfied by single bonds.
Thus, we have 2 types of alkanes:
• Aliphatic alkanes are alkanes with straight linear chain or branched chain whose general formula is CnH2n+2,
with n, a natural integer.
• Cyclic alkanes so called cyclanes are alkanes with ring structure and have general formula CnH2n
Natural occurrence of alkanes is wide but most are concentrated in petroleum oil and natural gases ( for example,
methane, propane, ethane and butane).
I.2 Nomenclature and isomerism
The saturated hydrocarbon form homologous series (series in which members have similar chemical properties
and each differs from the preceding by a methylene group –CH2 ).
The first four members are known by their common names, from C5 and above the Greece prefixes indicating
the number of carbon atoms is written followed by the desinence “ane” of the alkanes.
Note: Alkyl groups are obtained when one hydrogen atom is removed from alkanes; therefore their names are
deduced from the corresponding alkanes by replacing “ane” desinence with “yl” desinence.
n Name of residue R-H Alkane alkyl R residue abbreviation

1 Meth ane CH4 -yl CH3- Me
2 eth ane CH3CH3 -yl CH3CH2- Et
3 Prop ane CH3CH2CH3 -yl CH3CH2CH2- Pr
4 But ane CH3(CH2)2CH3 -yl CH3(CH2)2CH2- Bu
5 Pent ane CH3(CH2)3CH3 -yl CH3(CH2)3CH2- Pe
6 Hex ane CH3(CH2)4CH3 yl CH3(CH2)4CH2- Hex
7 Hept ane CH3(CH2)5CH3 yl CH3(CH2)5CH2- Hep
8 Oct ane CH3(CH2)6CH3 yl CH3(CH2)6CH2- Oct
9 Non ane CH3(CH2)7CH3 yl CH3(CH2)7CH2- Non
10 Dec ane CH3(CH2)8CH3 yl CH3(CH2)8CH2- Dec
11 undec ane CH3(CH2)9CH3 yl CH3(CH2)9CH2- ?
12 Dodec ane CH3(CH2)10CH3 yl CH3(CH2)10CH2- ?
13 Tridec ane CH3(CH2)11CH3 yl CH3(CH2)11CH2- ?
14
14 Tetradec ane CH3(CH2)12CH3 yl CH3(CH2)12CH2- ?

15 Pentadec ane CH3(CH2)13CH3 yl CH3(CH2)13CH2- ?
16 Hexadec ane CH3(CH2)14CH3 yl CH3(CH2)14CH2- ?
17 Heptadec ane CH3(CH2)15CH3 yl CH3(CH2)15CH2- ?
18 Octadec ane CH3(CH2)16CH3 yl CH3(CH2)16CH2- ?
19 Nonadec ane CH3(CH2)17CH3 yl CH3(CH2)17CH2- ?
20 icos ane CH3(CH2)18CH3 yl 㖻H3(CH2)18CH2- ?
21 Henicos ane CH3(CH2)19CH3 yl CH3(CH2)19CH2- ?
22 Docos ane CH3(CH2)20CH3 yl CH3(CH2)20CH2- ?
23 Tricos ane CH3(CH2)21CH3 yl CH3(CH2)21CH2- ?
. . … ……………………….. …. ………………...
.30 Triacont ane CH3 (CH2)28CH3 yl CH3 (CH2)28CH2- ?
40 Tetracont ane CH3(CH2)38CH3 yl CH3 (CH2)28CH2- ?
50 Pentacont ane CH3(CH2)48CH3 yl ……………….
60 Hexacont ane CH3(CH2)58CH3 yl ……………….
70 Heptacont ane CH3(CH2)68CH3 yl ……………….
80 Octacont ane CH3(CH2)78CH3 yl ……………….
90 Nonacont ane CH3(CH2)88CH3 yl …………………
100 hect ane CH3(CH2)98CH3 yl CH3(CH2)98CH2-
IUPAC Rules for Alkane Nomenclature
1. Find and name the longest continuous carbon chain.

2. Identify and name groups attached to this chain.
3. Number the chain consecutively, starting at the end nearest a substituent group.
4. Designate the location of each substituent group by an appropriate number and name.
5. Assemble the name, listing groups in alphabetical order.
The prefixes di, tri, tetra etc are used to designate several groups of the same kind and are not
considered when alphabetizing.
6. In case of chains of the same length, the priority is for the one of many branched alkyl groups.
15
7. For cyclanes, the prefix “cyclo" is recommended and then after the name of the alkanes of the same
carbon number. But in case of ramified cyclanes, the seniority is for the
3 CH3 CH3
1 5 4 3 2 1
2
CH3 CH CH3 CH CH2 C CH3
3 CH3 CH3 CH3

2-Metyl propane or isobutane
2, 2, 4-Trimethyl pentane
CH3 CH3 CH3
1 2 3 4 5 6 7 8
CH3 C CH3
CH3 C CH2 CH CH2 CH2 CH2 3C CH3
10 9 8 7 4
6 5 2 1
CH3 CH3 CH2CH3 9 CH2CH3
2,2-Dimethyl propane or neopentane 10
4-Ethyl 2,2,8,8 tetramethyl decane
not 7-Ethyl 2,2,9,9-tetramethyl decane
5 CH3 CH3
7 6 4
H H
3 2 1
CH3 CH2 C C C C CH3
H H
cyclobutane
CH3 CH2CH2CH3
cyclopentane
Cyclopropane
ring. :2,3,5 Trimethyl-4-propyl heptane
Note: If they are many than one subsitutient, then the numbering is done so that the sum of the numbers used to
locate the locants is minimum. This is the lowest sum rule.
(1) (2) (3) (4) (5) (6) L - R
CH 3 − CH − CH 2 − CH − CH − CH 3
6 |5 4 3| 2| 1 R -L
CH 3 CH 3 CH 3
The longest chain has 6 carbons, so it’s hexane chain. Sum of locants
a) L-R = 2+4+5=11
b) R-L = 2+3+5 =10
So since the sum of the locants for R-L numbering is minimum, then it is preferred
c) The name of the substituent is prefixed preceded by the locants to the name of the parent chain. Hence the
compound in c) is called 2,3,5- trimethyl hexane.
Table 3: Examples of cycloalkanes in different formula
Examples of Simple Cycloalkanes
Name Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane Cycloalkane
Molecular
C 3 H6 C4H8 C5H10 C6H12 C7H14 CnH2n
Formula
Structural (CH2)n
Formula
16
Line
Formula
Note: Iso, sec, neo and tert- prefixes are used before alkyl groups to designate a secondary or tertiary and quaternary
carbon attached to 2 or 3 identical or different alkyl groups respectively.
Isomerism: Alkanes show structural isomerism. The easiest way to find isomers is to draw the longest chain of carbon
atoms first and then reduce it by one carbon first until repetition begins to occur.
E.g. C6H14
(a) CH3-CH2-CH2-CH2-CH2-CH3 hexane (straight chain isomers)
(b) Then reduce the length by one gives 5 carbon atoms
CH 3 − CH − CH 2 − CH 2 − CH 3 (Branched chain isomer)
| : 2 - methyl pentane
CH 3
Note: The 6th carbon atom cannot be attached to carbon atom number 1 or 5, as this will make the longest chain of
carbon atoms still with 6carbons. It should be attached to a carbon atom in the middle.
(c)
CH 3 − CH 2 − CH − CH 2 − CH 3
| : 3 - methyl pentane
CH 3
(d) Longest chain reduced further to 4 carbon atoms
CH 3 − CH − CH − CH 3 -highly branched
| | : 2,3 - dimethyl butane
CH 3 CH 3
CH
3
(e) | : 2,2-dimethyl butane
CH − C − CH − CH
3 2 3
|
CH
3
Thus C6H14 has 5 isomers namely CH3-CH2-CH2-CH2-CH2-CH3,
CH 3 − CH − CH 2 − CH 2 − CH 3 CH 3 − CH 2 − CH − CH 2 − CH 3 CH 3 − CH − CH − CH 3
CH
3
| , , | | , |
CH 3
|
CH 3 CH 3 CH − C − CH − CH
3 2 3
CH 3 |
CH
3
Activity1: Give possible structure and provide their names according to IUPAC whose general formula is, C3H8,
C4H10, C5H12 and C7H16.
Notice: When the number of carbon increase, so closely the number of isomers increase as much as possible. This can
be summarized in the following table.
Table 4: Isomers in alkane series
Molecu
Molecula
lar Structural Isom Structural Isomer
Name r
Formul Formula ers Formula s
Formula
a
methane CH4 CH4 0 hexane C6H14 CH3(CH2)4CH3 5
ethane C2H6 CH3CH3 0 heptane C7H16 CH3(CH2)5CH3 9
propane C3H8 CH3CH2CH3 0 octane C8H18 CH3(CH2)6CH3 18
butane C4H10 CH3CH2CH2CH3 2 nonane C9H20 CH3(CH2)7CH3 35
17
pentane C5H12 CH3(CH2)3CH3 3 decane C10H22 CH3(CH2)8CH3 75
Eicosane C20H42 CH3(CH2)18CH3 36,448
Note: Structural isomers are molecules that have the same chemical formula, meaning they have the same atoms in
each molecule, but differ in the order in which the atoms are connected. The different order of the atoms produces
two completely different molecular structures.
Activity 2: From the above table, state and name these 18 possible structure of octane.
(i) Among these isomers, state and name the shortest molecule with one asymmetric carbon or chiral
carbon atom
(ii) State the isomers with 2 chiral carbon atoms and state whether are they optically active.
(iii) From the above results assigned in the table, can derive the generalized formula to calculate the
number of isomers from molecular formula of an alkane.
II.3 PHYSICAL AND CHEMICAL PROPERTIES
II.3.1 Physical properties
1. Alkanes occur naturally in mixtures of petroleum oil (crude) and as natural gases.
(2) Melting, boiling points, density and physical state
Table 5: Physical chemistry parameters about alkanes and their trends
Alkanes Melting Point 0C Boiling Point0C density Physical state

CH4 -182.6 -162.0 0.4240
C2H6 -172.0 -89.0 0.5463 gas
C3H8 -157.1 -44.0 0.5824
C4H10 -135.0 -0,5 0.5933
C5H12 -129.7 36.2 0.6264
C6H14 -94.5 69.0 0.6594
C7H16 -90.5 98.4 0.6837
C8H18 -57.0 125.6 0.7028
C9H20 -53.7 150.7 0.7179 Liquid
C10H22 -29.7 174.0 0.7298
…. …. …. ….
…. …. …. ….
C17H36 16.0 300.0 0.769
C18H38 28.0 309.0 0.7767 Solid and
elsewhere as n
increase
From the above table, it is remarkable that the boiling points, melting points of alkanes increase with the number of
carbon i.e. molecular weight.
Explanation: Boiling points depend on the magnitude of the Van Der Waal’s forces between the molecules. The
forces increase in magnitude with molecular weight. A plot of melting points against number of carbon atoms shows
that it does not fall on a smooth curve unlike the case of boiling points. In effect two curves are obtained for the
alkanes with even number of carbon atoms and those with odd numbers.
Alkanes with even numbers of carbon atoms have higher melting points than those with odd numbers closed. This is
because, the carbon chain for the even adopt a much closer parking than those for the odd so that the Van der Waal’s
forces are much greater for the event.
18
Note: Branched chain isomers have lower boiling points than their straight chain isomers.
n-pentane: Boiling point CH2 CH2 =360C
H3C CH2 CH3
Isopentane: Boiling H C CH2

point =280C
3
CH CH3
CH3
H3C
CH3
neopentane: Boiling point C =9.50C
H3C
CH3
Boiling points decrease with increase in branching because increased branching gives the molecule a more nearly
spherical shape and this reduces the extent of contact between neighboring molecules and hence the attractive force
between the molecules are reduced hence decrease in the boiling point.
Activity 3: Discus the trend of boiling points of C5H12 isomers.
Answer: The compounds pentane, isopentane, and neopentane all found in gasoline are structural isomers of C5H12:
The different arrangement of atoms gives each compound a distinct set of properties. For example, because pentane
molecules are longer than are isopentane or neopentane molecules, pentane molecules become more entangled with
each other. These entangled molecules require more energy to separate, for instance, from a liquid into a gas. As a
result, liquid pentane has a higher boiling point than that of isopentane or neopentane. In contrast, the spherically
shaped neopentane molecules separate from one another more easily, giving liquid neopentane a lower boiling point
than that of pentane or isopentane.
3. The lower alkanes are more volatile than heavy alkanes i.e. of high number of carbon
4. Solubility: They are not soluble in water, because of their low polarity and also because of their inability to form
hydrogen bonds. They are, however soluble in non polar solvents, like CCl4, CS2, benzene, and are miscible with one
another. Hence, their density is less than one.
19
II.3.2. CHEMICAL PROPERTIES
Alkanes are quite inert towards common reagents reason why their reactions are very few because:
(i) The C-C and C-H bonds are strong and do not break down easily
(ii) Carbon and hydrogen have nearly the same electro negativity value hence C-H bond is only slightly polarized
(iii) They have no unshared electrons to offer. They, however, undergo the following reactions.
1. Combustion of alkanes breaks down to carbon dioxide ( if oxygen is enough to burn all quantity of
hydrocarbons else, carbon monoxide is formed) and water.
3n+1 O2(g) n CO2(g) + (n+1)H2O(l) + heat released
CnH2n+2 +
2
Activity4: The complete combustion of 100 ml of gaseous mixture of methane and ethane produce 150 ml of
carbon dioxide.
Answer: 50ml for methane and 100 ml of ethane.
2. Reaction with halogens (halogenations)

R-H + X2 → RX+ HX avec X = Cl, Br, I
Note: In order to discus clearly
Mecanism :
i. phase 1 : Initiation(radical formation)

hν
Br2 → 2 Br •
ii. phase 2 :Propagation
CH 4 + Br • → •CH 3 + HBr
• CH 3 + Br2 → CH 3 Br + Br •
iii. phase 3 : Ending steps (Radical combinations)
CH3 • +CH 3 • → CH 3 − CH 3
CH 3 • + Br • → CH 3 Br
Br • + • Br → Br2
Hence, the generalized reactions product is like
Light(hv)
CnH2n+2 + X2 CnH2n+1X + HX
R-X
X2 : Can be Cl2, Br2 and in some case I2 but not F2
Notice: (i) Br2 reacts as Cl2 but slowly while iodine react hardly or do not while fluorine, the most electronegative
element of the periodic table reacts in order to give coke.
Light(hv)
CnH2n+2 + (n+1)F2 nC(S) +(2n+2) HF
(ii) Due to radical formation involved, the main products of reaction is the one from the most stable radical starting
with tertiary, secondary, primary and methyl in decreasing order of stability.
H
Cl2/sunlight CH3CH2CH2Cl + CH3 C CH3
CH3CH2CH3
30% Cl
70%
2. Nitration: RH +HNO3 ° RNO2 + H 2 O
425
→
20
Activity 6: Motivate the above reaction through mechanism in order to show how nitration of alkanes gives
nitroalkane and give secondary products of nitration.
4. Dehydrogenation of alkanes give alkenes under heat and a catalyst like V2O5.
CH2=CH2 + CH3CH3
V2O5
CH3CH2CH2CH3 CH3CH=CH2 + CH4
0
500 C
CH3CH2CH=CH2 + H2
Activity 7: From the reaction of combustion of alkanes, how can you motivate the air pollution resulting from
kerosene uses as energy source.
II.4. GENERAL METHODS OF PREPARATIONS OF ALKANES
(i) Reduction by addition of hydrogen ( hydrogenation) to alkenes and alkynes in the presence of catalyst like Nickel,
Palladium or platinum produces alkanes.
Ni Ni CH3-CH2-CH3
R-CH2-CH2-R' CH3-CH=CH2
R-CH=CH R'
150 0C 1500C
alkene Alkane Propene propane
H2/Ni
Note: Reduction with Platinum and Palladium, as catalyst occurs at room temperature while that Nickel requires a
temperature of about 1500C.
2. From halogeno alkanes or Alkyl halides

On reduction of alkyl halides with Zn and Concentrated hydrochloric acid, alkyl halides are converted to alkanes.
+
a) 2 RX + Zn →
H
2 RH + Zn 2+ + 2 X −
+
E X : CH 3 − CH 2 CHBr − CH 3 Zn
/ 
H
→ CH 3 CH 2 CH 2 CH 3
EX : CH 3 − CH 2Cl + Li → RLi CuX
→ R2 CuLi R→

'X
R − R'
CH3CH2Cl +Li → CH3CH2Li +CuI → (CH3-CH2)2CuI +CH3 (CH2)5CH2Br→CH3 (CH2)7CH3. n- nonane.
R − X + H 2 →
Pd
RH + HX
Ex : CH 3 − Cl + H 2 → CH 4 + HCl
Pd
 MgXOH 
RX + Mg  → RMgX 
Ether / sec
  → RH +  MgNH 2 X
H 2O / NH 3 / CH 3OH

 Mg (CH 3O ) X 
EX: CH 3 Br + Mg → CH 3 MgBr  → CH 3 − CH 3 + MgBr2
3 CH Br
b) Alkyl halides when heated with sodium metal in ether solution give higher alkanes (Wurtz reaction)
e.g.: 2CH 3CH 2 Br + 2 Na  → CH 3 − CH 2 − CH 2 − CH 3 + 2 NaBr

ether / heat
Note: This reaction is practically useful in organic synthesis to increase the length of carbon chain.
c) When Alkyl halides are treated with Zn-Cu couple, in the presence of ethanol, alkanes are formed.
21
E.g. CH 3CH 2Cl    

→ CH 3CH 3
ethanol / Zncouple
3. From carboxylic acids
When sodium salts, of carboxylic acids, are heated with soda lime, they eliminate a molecule of carbon dioxide
NaOH / ∆
gas to form alkanes. R − COOH  
→ RH + Na 2 CO3 + H 2 O
NaOH / ∆
Ex: CH 3 − COOH   → CH 4 + Na 2 CO3 + H 2 O
Note: The reaction is practically used to reduce one the length of carbon chain.
4. From carbonyl compounds
Reduction of carbonyl compounds, with amalgamated Zinc and HCl (Clémensen reaction)
(From aldehydes or ketones)
Ex : CH3CH2C=OCH3+     → CH 3 − CH 2 − CH 2 − CH 3 + H 2 O
Zn ( Hg ) / HClconc
Note: Under special conditions, reduction also is effected by use of H2 and Ranley Nickel or using hydrazine and
KOH through Wolf Kishner reduction.
Activity 8: Identify A and B.
Cl
2 Na H2/Heat
G D
Na
A+ B CH3CH -C CH3 + 2NaCl
CH3 CH3
II.5. USES
• Alkanes are used as energy sources like methane, ethane, propane and butane
• They are used as organic solvents of varnish, dyes, paint and extracting solvents like hexane for pyrethrin
((C22H28O5 or C21H28O3) contained in pyrethrum) extraction.
II.6.EXERCISES
I. Give all possible structure and their nomenclature according IUPAC of an alkane whose molecular formula is
C7H16
II. Suggest the structure of an hydrocarbon ( lowest alkane) that satify the following conditions:
(a) With at least one asymmetrical carbon i.e. carbon atom attached to four different substituents
(b) Its halogenations gives the same products and has the general formula C5H10
(c) The hydrocarbon belonging to saturated hydrocarbons that is more volatile than others.
(d) The insoluble alkane in water but used as more likely as organic solvents and is used in the industry of
treatment of pyrethrin.
(e) The hydrocarbons with two C* than can be obtained by wurtz procedure.
III.The complete combustion of a mixture of 100 ml of ethane and methane as the main natural gases release 150 ml
of a gas that turn milky the lime water under normal conditions.
(i) Calculate the volume of methane and ethane in the mixture
(ii) Calculate the volume of air that should be supplied for this process
(iii) Hence, calculate the molar fraction of each gas
Answer: (i) The volume of gases are equal to 50ml

(ii) Volume of air required is 687.5 ml
(iii) Molar fraction of both gases is 0.5 or 50%.
22
IV.The crude oil used after a series of treatment from rock up to kerosene as the energy source in terms of heat is a
mixture of two or more hydrocarbons which are heavy or light hydrocarbons in various physical state starting from
gas, liquid up to solid as the number of carbon atoms increase.
The laboratory quality control of the kerosene provides two predominant hydrocarbons A and B. The measured
density of A with respect to oxygen is 8.06 while the combustion of 284mg give 880 mg of carbon dioxide and
396mg of water.
(a) Define the term hydrocarbon.
(b) Give the molecular formula of A and B.
(c) Determine the volume of oxygen required for the combustion of B in the above mentioned conditions
(d) Give at least three isomers of A and B and their nomenclature.
(e) A as a pseudo liquid was treated with bromine solution which is yellow –orange and allow the light to pass
through it. After 10 minutes, there was a complete discharge of color and the blue litmus paper turns red.
(i) Discuss the above results in (e).
(f) How can you handle the preparation of A whether in the laboratory or in the industry from raw material.
(g) State the compound E, isomer of B with one chiral carbon atom which is a carbon that is attached to four
different substituents.
(h) Explain the comparison of boiling points of B and E.
(i) Complete the following reaction and identify each letter:
P
M
Na
V2O5/heat
F2/ligth Cl2/light
I+J B G
n
l/Z
HC HNO3/light
L
V. The combustion enthalpy of butane is -300KJ.mol-1. 1.2dm3 of butane (measured in standard condition) has been
used for boiling water from 200C to boiling point of water (1000C).
a) Write down the balanced chemical equation of combustion of butane (C4H10).
b) If the molar volume of any gas in standard condition (200c and 1atm as pressure) is 24 dm3, calculate
the molar number of butane contained in 1.2 dm3.
c) If 80% of the heat produced from combustion of 1.2 dm3 of butane were involved in heat exchange
during boiling of a given mass of water. Calculate the mass of mass of water that was boiled. (Specific
heat capacity of water is 4.2 J.g-1K-1).
d) If the enthalpy of combustion of hydrogen and carbon are -284KJ.mol-1and -394KJ.mol-1, calculate the
enthalpy of formation of butane.
VI. (i) The complete combustion of 10 ml of an alkane in gas state requires 50 ml of oxygen. Identify A.
(ii) The Complete combustion of of 25 ml of a mixture of propane and ethane produce 60 ml of carbon
dioxide (in standard condition). Calculate the molar fraction of each gases.
(iii) The laboratory analyses of an organic compound A provides 83.72% of carbon and 16.28% of
hydrogen and has a density of 2.70. Through halogenations A can give two alkyl halides. Give the
structure of A.
23
VII. Identify the compounds A and B that generates an alkane A through prescribed chemical reactions.
Compounds A Reactions Compounds B
Isobutene Reduction alkyne
n-hexane Wurtz Alkyl halides
Propane decarboxylation Carboxylic acid
n-pentane Clemmensen ketone
2,3-dimethyl butane electrolysis Sodium carboxylate
n-butane reduction Alkyl halides
Cyclohexane reduction alkene
CHAP III: ALKENES
III.1 Definition and introduction
Alkenes are hydrocarbons which have at least one double bond (C=C) and have two hydrogen atoms less than
alkanes and they are represented by a general formula CnH2n.
III.2 Nomenclature and isomerism
• In the IUPAC system of nomenclature, alkenes are named by replacing, ”ane” of the corresponding alkanes
with “ene” from alkene.
• The longest chain containing the double (C = C) bond is usually taken and the carbon atoms are then
numbered in such a manner which gives the least value to the carbon atom with the double bond.
CH2=CH2 : Ethene, CH3-CH=CH2: propene, CH3-CH2-CH=CH2: but-1-ene ,CH3-CH=CH-CH3:But-2-ene
Examples: 1. CH2=C-CH=CH2: 2-methyl buta-1,3-diène (nom usuel: isoprène)

|
CH3
CH2= CH-CH(CH2CH3)-CH2-CH2-CH(CH3)-CH2-CH(CH3)-CH2-CH3 : 3-Ethyl 5,7-dimethyl oct-1-ene
| |CH3
CH2-CH3 CH2-CH=CH2
3ethyl 6-(-2methyl) butylnona-1,8diene.
2. CH3-CH=CH2: Propene : ( propylene)
CH2=C-CH=CH2: 2-methyl buta-1,3diene ( isoprene)
|CH3
CH3-CH=CH- : 1-propenyl
CH2=CH- : Ethenyl or vinyle
Alkenes exhibit four types of isomerism due to the carbon number-hydrogen ratio.
1. Chain isomerism: Chain isomerism arises due to differences in the nature of the carbon chain.
Note: in chain Isomerism, the position of double bond does not change.
24
CH 3 CH 2 CH = CH 2 1 - butene ( straight chain isomer)

(i) C4H8 has
CH 3 C = CH 2 2 - methyl - 1 - propene (Branched chain isomer)
|
CH 3
(ii) C5H12 represents the following
CH 3 CH 2 CH 2 CH = CH 2 pent - 1 - ene ( straight chain isomer)
CH 3 CH 2 C = CH 2 2 - methylpbut - 1 - ene (Branched chain isomer)

|
CH 3
2. Position isomers: this isomerism arises as a result of different position taken by the double bond in the same chain:
Position isomers Name
CH 3CH 2CH = CH 2 but-1-ene
CH 3CH = CH -CH 3 but-2-ene

And
CH 3CH 2 CH 2 CH = CH 2 pent - 1 - ene
CH 3CH 2CH = CH - CH 3 pent - 2 - ene

Note: The positions of the double bond change but not the structure of the carbon chain.
3. Ring Isomerism: Both alkenes and cycloalkanes (hydrocarbons where the carbon atoms are arranged in a ring) are
isomeric.
Examples:
Formula Corresponding alkene Cycloalkane
H2C
CH2
H2C
C3H6 CH 3CH = CH 2 Propene

cyclopropane
CH 3CH 2CH = CH 2 but-1-ene

C4H8
CH3C = CH 2 2-methylprop-1-ene
|
CH3
H2C H2C CH2
CH CH3
H2C H2C CH2
2-methyl cyclopropane cyclobutane

CH 3CH = CH -CH 3 but-2-ene
4. Geometrical Isomerism: This type of Isomerism arises because of the inability of the double bond to allow free
rotation around it , therefore cis and trans isomers are possible
25
H H
H
CH3
C
H3C H
CH3 CH3
E.g. Trans But-2-ene Cis but-2-ene
Note: Trans isomer is thermodynamically more stable than cis isomer since their dipolar momentum is
zero.
III.3 PHYSICAL AND CHEMICAL PROPERTIES
III.3.1 Physical properties
1. Alkenes with carbon number less than 4 are gas at ordinary temperature, the other are liquid up to 18 while
others are solids as n increase
2. Boiling points and melting points of alkenes are less than those of alkanes but also increase as the molecular
weight increase.
3. Alkenes are insoluble in water but soluble in most organic solvents.
III.3.2 CHEMICAL PROPERTIES
Because of high concentration, of electrons around a double bond, it is stronger and shorter than a single bond.
Bonds Bond Dissociation energy Bond length
C-C 346kJ.mol-1 0.154 nm
C=C 612kJ.mol-1 0.134nm
Because of high electron density around the double bond, alkenes will tend to react with reagents which are electron
seeking (electrophiles).
3.2.1Addition reactions
Alkenes undergo reactions in which the double bond is converted to a single bond since
(a) Addition of hydrogen (Reduction or hydrogenation)
This reaction occurs in the presence of a catalyst like Ni, Pt or Pd.
Ex: R − CH = CH − R '+ H 2 → R − CH 2 − CH 2 − R '
Pt
Note: This reaction is of much practical importance because:

• It is used in the synthesis of saturated hydrocarbons compounds for example in the manufacture of
margarine
• In thermochemistry it is used to determine the stability of the alkenes
CH 3CH = CH − CH 3 + H 2 
Pt
→ CH 3CH 2CH 2CH 3 ∆H = −28.6kCal
Cis
26
CH 3CH = CH − CH 3 + H 2 
Pt
→ CH 3CH 2CH 2CH 3 ∆H = −27.6kCal
Trans
Hence Trans but-2-ene is more stable than its Cis isomer.
(b) Addition of halogens

Alkenes react by addition reaction with halogens to produce dihalogéné products.
Ex: H2C==CH2 + Br2 → BrH2C-CH2Br
Mechanism:
_
+ Br Br
C C + Br-
+
Br
Br
C C
Br
Trans addition
Br
CCl4
+ Br2
Br
Note: When halogenations is carried out in the presence of water (e.g with bromine or chlorine water ) the product
obtained is as below.
CH 2 = CH 2 + Cl
2 /→ Cl − CH 2 − CH 2 − OH
H 2O
CH 2 = CH 2 +   → Br − CH 2 − CH 2 − OH
Br2 / H 2O
[ ] −
Now because water is presented in excess H 2O > Cl  , the carbanium is attacked by H 2O and not Cl- since
Oxygen is more electronegative than chlorine but also H2O react with chlorine to give HOCl and HCl.
(ii) The reaction of alkenes with bromine is used as a test for instauration (Presence of a double bond).In this reaction
decoloration of bromine indicates presence of multiple bond for example a double bond.
(iii) In this reaction, the halogens are called electrophiles or electrophilic reagents. They are electron deficient
species, which react by seeking electron rich substances. Electrophiles are two types:
• Positive electrophiles are those which carry positive charges and include H+ cations and carbonium ions.
• Neutral electrophiles: These do not carry charge e.g. AlCl3 , ZnCl2, BF3 which are acids according to
Lewis definition
(C) Addition of halogen acids

Alkenes react with aqueous solution of halogen acids to produce alkyl halides in the absence of peroxide at
room temperature through ionic mechanism while elsewhere i.e. in the presence of peroxide and or high
27
temperature, alkyl halid is formed but with different position as in the first case since this respects radical
mechanism as shown in the closed scheme:
X
C C
H2SO4
C C + HX H
C C
X
H H
H3 C C C H (99%)
H H
Cl H
H2SO4
C + HCl
CH3 H
H H
H3C C C Cl (1%)
H H
CH 3 − CH + − CH 3 sec ondary carbanium
Note: (i) In this reaction, two carbanium ions are possible.
→ CH 3 −CH 2 − CH 2 + primary carbanium
Here the reaction proceeds via a more stable secondary carbanium ion since tertiary is more stable than secondary
which is also more stable than primary carbanium ion.
(ii) In these reactions, the electrophiles is the halogen acid with H atom carrying a partial positive charge. The
product of this reaction is predicted by use of Markovnikov’s rule. This rule states that:
in addition reactions involving unsymmetrical alkenes (alkenes where the carbons atoms carrying double bond have
different number of hydrogens), the Hydrogen of the halogen acid is added to the carbon which carries the greater
number of hydrogen atoms while the halide atom adds the one with the lesser.
By contrast, in the presence of peroxide (ROOR) or and at high temperature, the reaction proceeds via free radical
mechanism, and the product of reaction is predicted by anti Markov nikov’s rule which state that HBr addition only.
28
H H
H3C C C H (99%)
H H
Cl H
H2SO4 Markov
C + HCl nikov
CH3 H process
H H
H3C C C Cl (1%)
H H
H H
H3C C C H (1%)
H H KARASH
peroxide Cl H
effect
C + HCl
H2O2
H
CH3
H H
H3C C C Cl (99%)
H H
Mechanism
Peroxyde / ∆
CH3-CH2-CH=CH2 +HBr  → CH 3 − CH 2 CH 2 CH 2 Br
∆
R-O-OR 
→ 2R − O •
H
CH3CH2 C CH2Br secondary

. . radical: more
CH3CH2 CH CH2 + Br H stable
CH3CH2 C CH2 primary

radical
unstable
Br
HBr
H H
CH3CH2 C CH2Br CH3CH2 C CH3
H Br
90% 10%
Note: (i) Addition of HF, HCl and H-I in the presence of peroxide is not affected. Product is predicted by use of
Markownikov’s rule due to their high reactive of fluorine and chlorine while iodine is less reactive.
(ii) Free radical is an atom or a group of atoms with an unpaired electron.
d. Hydratation of alkenes: preparation of alcohols

Alkenes react with sulfuric acid to form alkyl hydrogen sulfate. On diluting the product (alkyl hydrogen sulfate) and warming
an alcohol is produced.
29
H2O R-CHOH-CH3
R-CH=CH2
H2SO4
CH3CH=CH2 H2O CH3CHOH-CH3
H2SO4
OH
H2O
H2SO4
Examples:
1.Akene protonation + H+
+
alkene H
_
2. Water attacks carbocations: + O
+ _
H H H +
H O
_ H
H
deproto
nation
H+ +
. H OH
. . Catalyst
alcohol
e. Reaction with oxygen.

R R'''
R
R'''
1 Ag
+ O2
2 1700c R''
R' R'' R' O
Epoxide
f. Reaction with ozone or ozonised oxygen (O3)
R R R'
R' Zn/H O 2
+ O3 O + O
+ H2O2
R''
R''' R'' R'''
This reaction goes through molozonide, then ozonide and finally hydrolysis gives carbonyl compounds.
30
R O R'
R'
R
R' O3
R
R'''
R''' R''
R'' O O
R''' O O
R'' ozonide
_O
Zn/H2O
Molozonide
R R'
O + O
R'' R'''
R R'
R
R' Oxidizing agent
O + O + H2O2
R' R''
' R''' R'''
Note:
(a) Conversion of an alkene to aldehydes or ketones.
(b) The products of ozonolysis and subsequent by hydrolysis are used to determine the
structure of alkenes that is to determine the position of the double bond C=C.
(c) Due to the fact that in case of aldehydes formation above, in the presence of excess
quantity H2O2 already formed it is remarkable that aldehydes can be oxidized to carboxylic acid R-COOH.
2. Oxidation Reaction
(i) Alkenes undergo oxidation reaction by mild oxidizing agents like alkaline potassium permanganate to form diol.
Note: The purple color of the potassium permanganate is discharged and this reaction is also used as a test for the presence of
R R
R' R'
dilute KMnO4
Warm
R'' R''
R''' OH OH R'''
Diol( Cis hydroxylation)
OH
Dilute KMnO4
Warm
double bond. OH
(ii) By contrast, With strong oxidizing agents like acidified KMnO4 , potassium dichromate K2Cr2O7 under heat condition, the
double C=C is broken down and oxygen atom is fixed on both two carbon atoms carrying the double like in ozonolyzis
process above discussed.
(iii) Combustion of alkenes produces carbon dioxide and water.

3n n CO2 + n H2O
CnH2n + 2 O2
31
3. Polymerization
Compounds having double bonds can combine repeatedly two or more times to form long chain molecules. The
reaction is called polymerization. If Z is monomer unit them on combination, so many repeated units of Z will be in
the product called the polymer.
Z-Z-Z--Z-Z-Z-Z-Z-Z-Z-Z-...........Z
nZ
monomer
unit polymer chain
Polymer, substance consisting of large molecules that are made of many small, repeating units called monomers. The
number of repeating units in one large molecule is called the degree of polymerization. Materials with a very high
degree of polymerization are called high polymers. Polymers consisting of only one kind of repeating unit are called
homopolymers. Copolymers are formed from several different repeating units.
4. Polymerization :
* Radical initiators: R-O-O-R → 2R-O •
hv
R O + H2C CH R O CH2 CH
2. R R
H2C CH
R
R O CH2 CH R O CH2 CH CH2 CH
3. R R R
R1 O CH2 CH
+ HC CH2 O R2 R1 O CH2 CH CH CH2 O R2
R R R R
Note: Polymers will be more developed in the module of senior six chemistry combinations.
Table6: Summary of most alkene polymers obtained from alkenes as monomers and their properties and uses
Polymers Monomers Properties Uses
Polyethylene(PE) CH2=CH2 Thermoplastic, translucent, permeable Films, bags, pipe and
-(CH2-CH2-)n- to by hydrocarbons, alcohol, resistant to tubind, insulating
X-ray and Chemical agent. gloves, bottle stoppers,
lids and plastic wraps
32
Polypropylene(PP) CH3-CH=CH2 Thermoplastic, low density, durable and Household items,
-(CH3- CH-CH2)n- resistant to X-ray, permeable to water, plastic wraps,
impact resistant and temperature automobile parts,
resistant to 1350C. batteries, garden
furniture, syringes,
bottle appliance.
Polystyrene(PS) C6H5-CH=CH2 Thermoplastic, transparent, resistant to plastic wraps, kitchen
(C6H5-CH-CH2)n X-ray and oils, nontoxic, optical and utensils, furniture covers
electrical properties, easy to color thermal insulation, toys
and office supplies,
disposal razors.
Poly vinyl chloride CH2=CHCl Thermoplastics, soft or rigid, opaque or Household items,
-(CH2-CHCl)n- transparent, fire resistant, resist to X-ray, Electrical wire insulation
acids, bases, oils, grease and alcohol Water pipes, floor
Coverings, window and
door covers, items for
chemicals and industry
sports.
Polytetrafluoro CF2=CF2 Chemically inert, antiadhesive, resistant Orthopedic and pro-
Ethylene(PTFE) to corrosion and heat, impermeable to sthetic appliances,
-(CF2-CF2)n- water. Hearing aids, corrosion
resistant and mechanical
parts, upholstery, joints,
flying pan coatings,
electric insulation.
33
Natural polymers resulting from alkenes as well as natural rubbers were not discussed because their formation mechanism are
not yet thought and other natural alkenes like isoprene generates terpenes, terpenoids which are characterized during
screening.
III.4 General methods of Preparations
Alkenes are generally synthesized by elimination or addition reactions from saturated and unsaturated
compounds respectively through the following scheme:
Elimination(-AB)
H2/Pd*
C C C C C C
Addition(+AB) -H2/heat
A B CH2- Alkynes
alkenes
1. By the reaction between halogenoalkanes (alkyl halides) with hot alcoholic alkali solution. In this method, the
alkyl halide is boiled with aqueous KOH in the presence of alcohol.
−
Ex : → CH 2 = CH 2 + H 2 O + Br −
CH 3 − CH 2 Br OH
−
CH 3 − CH 2 − Cl NH
 2
→ CH 2 = CH 2 + H 2 O + Br −
This reaction is called elimination reaction because the alkyl halide loses a molecule of hydrogen halide(HX like
HCl, HBr, etc).
Note: (i) The reaction above with bromoethane (primary alkyl Halide) occurs by elimination Bimolecular E2
mecanism .
(ii) Reaction of a tertiary alkyl halide under same conditions as above occurs by elimination unimolecular E1.
Br
|
CH 3CH 2O − Na + / ethanol /heat
Ex: CH 3 − C − CH 3        → CH 2 = C − CH 3 + NaBr
| |
CH 3 CH 3
Note: (i) The reaction is favored by use of high temperature and presence of strong base.
(ii) Since the rate of reaction will depend on the strength of the carbon-halogen bond, it will be fastest with
iodo compounds and slowest with Chloro compounds. Hence the order of bond strength is C-Cl > C-Br >C-I.
2. By the reaction between alcohols and hot H2SO4 or H3PO4 in liquid phase.
(a) Liquid phase
+
Ex: R − CH 2 − CH 2 − OH + H  → R − CH = CH 2 + H 2 O
T
Note: A carbanium ion is a cationic species in which a positive charge is located on a carbon atom. There are 3types of
carbanium ions called tertiary, secondary and primary carbonium ions
Because all alkyl groups ( R-) are electron donating species (have positive inductive effect), the positive charge on the carbon
atom in the tertiary carbanium is highly neutralized and this makes it the most stable while the least stable is the primary
carbonium ion since it has only one such groups.
Therefore dehydratation of both butan-1-ol and butan-2-ol gives same product but-2-ene.
0
CH 3CH 2CH 2CH 2 − OH 
ConcH 2 SO4 /180 C
→ CH 3CH 2CH = CH 2 min or product
CH 3CH = CH − CH 3 major product
Note: During the elimination process leading to many alkenes suggested by the mechanism according to the
carbocations formation, the most stable alkene is the one with the most stable i.e. with double bonds most substituted.
This is commonly known as Zaïtsev’s elimination.
34
H CH3CH=CH-CH3
99%
CH3CH2 C CH3
OH CH3CH2-CH=CH2
1%
(b) Vapour phase: in this method, the vapour of alcohol is passed over heated aluminium oxide as catalyst.
CH3CH 2CH 2 − OH 

Al2O3 , heat
→ CH3CH = CH 2 + H2O
Note: Because the alcohol loses a molecule of H 2O, the reaction is called elimination.
3. By dehalogenation of vicinal –dihalides.
Vicinal dihalides are halogen compounds with two halogen atoms on adjacent carbon atoms while gem dihalides
have the two halogen atoms on the same carbon atom, here the vicinal is heated with Zn in alcohol.
E.g.: CH 3 − CHCl − CHCl − CH 3 + Zn 3 

→ CH 3 − CH = CH − CH 3 + ZnCl 2
CH OH / heat
Note: (i) Besides Zn, metallic sodium is also used.
CH 3 − CHCl − CHCl − CH 3 + 2 Na 
→ CH 3 − CH = CH − CH 3 + 2 NaCl
(ii) In the same reaction, with gem dihalides, higher alkanes are produced. This reaction is useful in organic
synthesis to increase the length of the carbon chain.
2 RCHX 2 + 2 Zn   → RCH = CHR + 2 ZnX 2
Alcohol / heat
e.g. 2CH 3CHCl 2 + 2 Zn    → CH 3CH = CHCH 3 + 2 ZnCl 2

Alcohol / heat
2CH 3CHCl 2 + 4 Na 
→ CH 3CH = CHCH 3 + 4 NaCl
4. Partial reduction of alkynes

Here the alkynes and the hydrogen in equimolar ratio are passed together over a heated catalyst like Ni, Pt or Pd.
R -C ≡ C − R + H 2 → RCH = CHR
Pd
5. Cracking of heavy hydrocarbons (alkanes) during petroleum treatment.

C12H32 C2H4 + C3H6 + C10H22
heat Ethylene
III.5 USES
• Alkenes, obtained from olefins are mainly used in polymers synthesis like polyethylene,
polypropylene, synthetic rubbers which are thermoplastic, thermosetting and other resistant
material to rust and corrosion. These polymers play a key role in our everyday life.
• Alkenes are used in alcohols, acetylene alkyl halides preparations
35
III.6 EXERCISES
I. (a) Assign the IUPAC names to the following alkenes :

• CH2=CH2
• CH2=C(CH3)-CH2-CH3
• CH3-CH=CH-C(CH3)3
• CH2=C(C2H5)-C(CH3)2-CH2-CH3
(b) Give the chemical structures that respond to the following names:
• Pent-2-ene
• 3-methyl but-1-ene
• Isobutene
• Cyclohexene
• Buta-1,3-diene
(c) Give all alkynes structure isomers with five atoms of carbons
(d) The same issues as above but for C4H4
II.(a) The complete combustion of 40 ml of a mixture of propane and propene requires 192.5 ml of oxygen.
Determine the percentage of each gas in the mixture.
Answer: propene : 37.5% and 62,5% for propane
(b) The vapour density of a mixture of ethene and propene is 1.05 within respect to oxygen.
Answer: 60% for ethene and 40% for propene
(c) 0.1 mol of an alkene A was ozonized with air and 0.1 mol of acetone(CH3-CO-CH3) and 0.1 mol of
propanal(CH3-CH2-CHO). Give the name of A.
Answer:A is 2-methyl pent-2-ene
(d) The complete combustion of 10 ml of an alkene A requires 90 ml of oxygen and produce 60 ml of carbon dioxide. A was
treated with strongly acidified potassium permanganate under heating conditions and produce butan-2-one(CH3-CH2-CO-CH3
and one mole of acetic acid(CH3-COOH). Identify A.
Answer: A is 3-methyl pent-2-ene
(e)Through exhaustive hydrogenation of an hydrocarbon A with molecular formula C9H16, A fixe 2 moles of hydrogen once
catalyzed with Platinum as a powder. By strong oxidation, A give acetone(CH3-CO-CH3), succinic acid(HOOC-CH2-CH2-
COOH) and acetic acid(CH3-COOH). Identify A.
Answer: CH3)2C=CH-CH2-CH2-CH=CH-CH3.
(f) An alkene A reacts with hydrobromic acid to give B which contain 48.5% of bromine. A part from that A reacts acidified
dichromate potassium to gave one compound D. Identify A, and B and D.
Answer:CH3-CH2-CH=CH-CH2-CH3 with cis and trans isomers but reject cis for more precision.
III. Complete the following chemical reaction in alkene series:
I
J
G
CH2N2
Br2 H
C lO
light
K2Cr2O7/H+ HBr/H2O2 KOH H2O
F Hex-3-ene A L M
Heat
2O
HCl/250c
Heat H2SO4
H2
3 /H
/N
O
D B N
C
Identify the isomers of N
36
CHAP IV: ALKYNES
IV.1. Introduction
Alkynes are hydrocarbons which contain at least a triple bond (C ≡ C) and they conform to the general formula CnH2n-2 with n,
a natural number greater than one.
Therefore, they are divided into 2 classes:
• Terminal triple bond is one at the end of the chain e.g.: : R-C ≡ C − H
• Internal triple bond is one in the middle of the chain: R − C ≡ C − R '
IV.2 Nomenclature and isomerism
According to the IUPAC nomenclature the ending “ane” of the corresponding alkane is replaced by “yne”
Examples: C2H2: Ethyne or acetylene

C3H4: Propyne
CH 3 − C ≡ C − C (CH 3 ) 2 − CH 3 : 4,4-dimethyl pent-2-yne
CH 3 − C ≡ C − C ≡ C − CH 2 − CH 3 : Hept-2,4- di yne
CH 2 = CH − CH 2 − CH 2 − C ≡ C − H : hex-5-ene-1-yne
Note: In the case of any molecule that contain at the same time double and triple bonds, double bond takes priority on triple
bond when assigning number but the compound is named as alkyne.
7 6 5 4 3 2 1
: Hept-2-en-6-yne
E.g. : HC C CH2-CH2-CH=CH-CH3
Alkynes except ethyne and propyne exhibit three types of isomerism such as:
(a) Chain isomerism: This arises due to different chain structure while the triple bond position doesn’t change.
Ex: Molecular formula C5H8 represents CH3CH2CH2C ≡ CH (pent-1-yne straight chain isomer)
4 3 2 1
H
H3C C C C H :3-methyl but-1-yne
and CH3 (branched chain )

(b) Position isomerism: This arises due to different position of the triple bond in the same chain.
Ex: C4H6 represents CH 3 − CH 2 − C ≡ C − H and CH 3 − C ≡ C − CH 3

(C) Function isomerism: Alkynes shows functional isomerism with dienes (alkenes with two double bonds) or cycloalkanes
with double ring or cycloalkanes with one double bond.
E.g. C4H6 represents CH 3 − CH 2 − C ≡ C − H and CH 2 = CH − CH = CH 2 (buta-1,3- diene)
: cyclobutene CH3 3-methy

cyclopropene
Note: Unlike alkenes, alkynes do not show geometrical isomerism because the molecule around the triple bond is linear.
Activity 1: Give and name according to IUPAC all possible structural whose molecular formula is C4H6. Define also
their relationships in terms of isomers.
37
IV.3 PHYSICAL AND CHEMICAL PROPERTIES
IV.3.1 Physical properties
(i) The first three are gases up to C4H8, other are liquid up to C15H28 and the rest are solid at room temperature
(ii) Alkynes are easily liquefiable and more soluble in water than corresponding alkanes and alkenes, and also some are
soluble in organic solvent.
(iii) Their boiling, melting points are higher than these of alkanes and alkenes of the same number of carbon.
(iv) Acetylene gas is usually stored in metal tanks, under pressure, dissolved in liquid acetone.
IV.3.2 Chemical properties
Due to the the presence of triple bonds, alkynes exhibit addition reaction on the triple bond in order to transform it in saturated
compound but also oxidation that break down triple bonds. Due to the fact that energy bond of triple bond is higher than the
one of double it requires much energy to break it down and closely alkynes are less reactive than alkenes.
1.1.1 Addition reaction

(i) Electrophilic addition reactions
Alkynes generally resemble to alkenes in undergoing addition reactions with electrophilic reagents; here two moles of the
reagent are added in two steps.
(a) Addition of Halogens: X2 (X=Cl , Br, I2)
Alkynes add one or two moles of halogens producing dihalides and tetrahalides respectively.
− C ≡ C − + X 2 → −CX = CX − →
X2
−CX 2 − CX 2 −
(b) Addition of halogen acids (HX)
This reaction is similar to that of alkenes. The product is predicted by use of Markov nikov’s rule where addition of one mole
of a HX produces unsaturated alkyl halide which then immediately adds another molecule of halogen acid to produce the
dihalogen compound. This is used to prepare gem dihalides.
EX: − C ≡ C − + HX → −CX − CH − →
HX
−CX 2 − CH 2 −
(ii) Addition of water
Alkynes react with water in the presence of sulphuric acid and mercury (II) sulfate at about 600C to give carbonyl compounds
after molecular rearrangement via tautomeric equilibrium as shown below .
Ex.
2+
CH 3 − CH 2 − C ≡ CH + H 2 O H  → CH 3 − CH 2 − CH (OH ) = CH 2
2 SO4 / Hg
←
Tautomeric equilibrium
→ CH 3 − CH 2 − CO − CH 3 : Ketone.
Note: The above equilibrium is known as tautomeric equilibrium which is also another kind of isomerism.
Activity 2: Suggest the plausible mechanism of the above reaction and explain why a ketone is more predominant
than an enol.
38
(iii) Addition of hydrogen
Alkynes combines with hydrogen gas in presence of suitable catalyst like finely divided Ni, Pt, or Pd . This reaction
initially produces alkenes which then take up another molecule of hydrogen to form alkanes.
− C ≡ C − + H 2 Pt/ Ni/
Pd
→ −CH = CH − →
H2
−CH 2 − CH 2 −
(iv) Reaction with ammoniacal silver nitrate or copper (I) Chloride
(a) Ethyne passed through a solution of ammoniacal silver nitrate deposits a white precipitate of silver dicarbide.
H − C ≡ C − H + 2 AgNO3 
NH 3
→ Ag − C ≡ C − Ag ↓ +2 NH 4 NO3
(b) Ethyne passed through a solution of ammoniacal copper(I) Chloride deposits a red precipitate of Copper (I) dicarbide.
H − C ≡ C − H + 2CuCl 
NH 3
→ Cu − C ≡ C − Cu ↓ +2 NH 4Cl
Note: Reaction (a) and (b) above are used to
(i) Differentiate Ethyne from ethane. The reactions show that the hydrogen atoms in Ethyne are slightly more acidic unlike
those in ethane.
(ii) Differentiate an alkyne with a terminal triple bond from that with an internal triple bond. Test for presence of a triple bond
. Only 1-alkynes will give positive test.
(V) Cyanidation
This is the reaction of alkynes with HCN which produces nitrile with double bonds.
R C C R' +H CN R C C R'
CN H
Activity 3: How can you differentiate the isomers whose general formula C4H6.
3.3.2 Oxidation Reaction

a. R − C ≡ C − R ' 
Strong Oxydizing agent
→ RCOOH + R ' COOH
This can be done only in the presence of strong oxydizing agent like chromic acid H2Cr2O4 or strongly acidified
potassium permanganate at high temperature.
(b) The combustion of alkynes produce carbon dioxide and water with given off a greater amount of energy in terms of heat.
Particular to acetylene, the flame of acetylene in UV-spectrometer can have temperature raising between 20000C and 30000C.
3n − 1
CnH2n-2 + O2 → nCO2 + (n − 1) H 2O + heat
2
3.3.3 Acidic properties of alkynes
σ−
i. R − C ≡ C − H σ + + Naσ + NH σ − 2 
NH 3liquid
→ R − C ≡ C − Na + NH 3
ii. R − C ≡ C − H + R ' MgX ( → R − C ≡ C − MgX + R ' H
C2 H 5 ) 2 O
1
iii. R − C ≡ C − H + Na → R − C ≡ C − Na + H 2 ↑
2
R C C H + R'-X R C C R' + HX
(iv)
Note: Products of these reactions above can be used for preparing higher alkynes. This is done by reacting the alkynide or
acetylides formed with alkyl halides.
1 ↑
e.g H − C ≡ C − H + Na → H − C ≡ C − Na +
NH3
H2
2
39
H − C ≡ C − Na + CH 3 − Cl → H − C ≡ C − CH 3 + NaCl
CH 3 − CH 2 − C ≡ C − Na + CH 3 − CH 2 − Br → CH 3 − CH 2 − C ≡ C − CH 2 − CH 3 + NaBr
3.4. Polymerisation
Alkynes can be heated at high temperature and produce aromatic compound starting with benzene.
H H
H C H
H
C C
H
C
H H
H H
C Benzene: C6H6
C H
H
Acetylene transitional structure
IV.4 General methods of preparation
1. From dihalogen compounds In this method, the dihalogen compound is refluxed with excess alcohol potassium
hydroxide solution. The dihalogen compound loses two moles of HX. I.e two moles of halogen acids are eliminated.
− CHX − CHX   2 OH − or 2 NH 2 −
 → −C ≡ C −
− CH 2 − CX 2 
Ex : CH 3 − CHBr − CH 2 Br  → CH 3 − C ≡ CH + 2 NaBr + 2 H 2 O
2 NaOH
Ex: CH 3 − CHBr − CH 2 Br   2 → CH 3 − C ≡ CH + 2 NaBr + 2 H 2 O

2 NaNH
Note: NaNH2 is more useful for preparing a terminal alkyne and KOH for internal triple bond alkynes because once
alkynes with ending triple bonds are heated with KOH, they are transformed to alkynes with internal triple bonds
which is more stable. This is known as isomerism reaction.
Ex : CH 3 − CH 2 − CHBr − CH 2 Br 
→ CH 3 − CH 2 − C ≡ CH 
→ CH 3 C ≡ C − CH 3
KOH KOH
CH 3 − CHBr − CHBr − CH 3 NaNH

2 → CH 3 − C ≡ C − CH 3 NaNH
2 → CH 3 − CH 2 − C ≡ CH
2. The second method is mainly for the preparation of acetylene (ethyne)
(a) Here calcium oxide oxide obtained by heating calcium carbonate is heated together with coke to a temperature of about
20000C in an electric furnace.
3C + CaO → CaC2 + CO + 112kCal

0
2000 C
The calcium dicarbide is then hydrolyzed
↑
CaC2 + 2 H 2 O → C 2 H 2 + Ca(OH ) 2
(b) Ethyne is also prepared (industrially) by heating methane to 15000C
°C
2CH 4 1000
 → C 2 H 2 + 3H 2
3. Alkylation of acetylene or terminal alkyne
H − C ≡ C − H → R − C ≡ C − H → R − C ≡ C − R'
Acetylene Terminal alkyne internal alkyne
40
i) With NaNH2: H − C ≡ C − H 2 → HC ≡ C − Na + NH 3

NaNH
H − C ≡ C − Na →
RX
H − C ≡ C − R + NaX
H − C ≡ C − R NaNH
2 → Na − C ≡ C − R R→

'X
R '−C ≡ C − R
ii) With organomagnesian ( RMgX)

H − C ≡ C − H RMgX
→ H − C ≡ C − MgX + RH
H − C ≡ C − MgX → RX
H − C ≡ C − H + MgX 2
H − C ≡ C − R → XMg − C ≡ C − R + R ' H
R ' MgX
MgX − C ≡ C − R →  R '−C ≡ C − R + MgX 2

R'X
Activity4 : State the steps by which but-1-yne can be prepared from inorganic compounds.
IV.5 USES
Alkynes are widely used in many industrial processes:
• Acetylene burns in air with a hot and brilliant flame and was formerly much used as an illuminant and is
now mainly used in the oxyacetylene torch, in which acetylene is burned in oxygen, producing a very hot
flame used for welding and cutting metal.
• Acetylene is also used in chemical synthesis, particularly in the manufacture of vinyl chloride for plastics,
acetaldehyde, acetic acid acetone and the neoprene type of synthetic rubber.
IV.6 EXERCISES
I.Give the names of the following molecule according to IUPAC rule 2009-July.
CH2CH3
(a) HC C CH2CH3 (c) (CH3)3C C C CH

H
(b) H3C C C CH
CH3
CH3 H
(d) CH3CH2 C CH=CH-CH3
CH3
C CH
(e) (f)
H3C
II. Give the chemical structure of the following molecule:
(a) Oct-3-yne (b) 2,2-dimethyl hex-3-yne
(b) Diethylacethylene (c) 3-methyl but-2-en-4-yne
(c) 2,2,5-trimethyl hex-3-yne
(d) Cyclobutyne
(e) Ethyt isopropyl acetylene
41
III. Give all possible structure of the compounds with molecular formula C5H8, C6H10, C4H6.Please name them according to
IUPAC rule.
IV. An hydrocarbon A with a density of 1.86 with respect to air. A give a white precipitate once treated with silver nitrate in
ammonia solution while a reddish precipitate is formed once treated with copper(I) chloride in the solution of ammonia
solution.
Answer: A is but-1-yne.
V. The complete combustion of a mixture of 50 ml of three gases such as propane, ethene and propyne requires 190 ml of
oxygen and produce 125 ml of carbon dioxide.
(a) Calculate the volume of each gas
(b) Calculate the percentage of each gas in the mixture
Answer: 15ml for propane, 25ml for ethene, 10 ml of propyne.
Show that it is impossible to determine volume of each gas if an alkane, alkene and alkyne have the same
condensation in carbon or have the save the same number in hydrogen.
VI. The complete combustion of 10 ml of an alkyne requires 70 ml of oxygen. A can be oxidized by chromic acid
give acetic acid (CH3-COOH).
Answer: pent-2-yne
VII. Complete the following chemical reaction of these compounds
H2O Br2/hv NaNH2 H2CrO4
CH3CH2CH2OH A B C D
H2SO4
Br2 KOH HBr
Ethene A B C
Br2 NaNH2 H2O
Propene A B C
VIII. How can you perform the following conversion from inorganic compounds to :
(a) propyne (d) CH3-CH2-CBr2-CHBr2
(b) but-2-yne (e) CH3-CH2-CHO
(c) cis but-2-ene (f) CH3-CBr2-CH3.
IX. An hydrocarbon A whose molecular formula is C6H10 has been treated with hydrogen under nickel powder as
catalyst and give n-hexane while treated with acidified solution of mercury (II) sulfate give a compound B of the
formula C6H12O. But the exhaustive oxidation of A with chromic acid gives propanoic acid (CH3CH2-COOH).
Answer: A is hex-3-yne
X. How can you distinguish the following compound through chemical tests (state the reagent that can be used,
condition and hence give the reaction if possible).
(i) but-1-yne and but-2-yne (v) hex-2-ene and hex-3-ene
(ii) but-1-yne and but-1-ene (vi) hex-3-yne and hex-2-yne
(iii) propane and propene (vii) but-1-yne and butane
(iv)isomer of C3H6 (viii) but-2-yne and butane.
42
CHAP V: PETROLEUM AND ITS ENGINEERING CHEMISTRY
V.1 Introduction
Petroleum, or crude oil, naturally occurring oily, bituminous liquid composed of various organic chemicals. It is
found in large quantities below the surface of Earth and is used as a fuel and as a raw material in the chemical
industry. Modern industrial societies use it primarily to achieve a degree of mobility on land, at sea, and in the airthat
were barely imaginable less than 100 years ago. In addition, petroleum and its derivatives are used in the manufacture
of medicines and fertilizers, foodstuffs, plastics, building materials, paints, and cloth and to generate energy in terms
of electricity.
V.1.1 Petroleum origin and formation
Petroleum is formed under Earth’s surface by the decomposition of marine organisms. The remains of tiny organisms
that live in the sea and, to a lesser extent, those of land organisms that are carried down to the sea in rivers and of
plants that grow on the ocean bottoms are enmeshed with the fine sands and silts that settle to the bottom in quiet sea
basins.
Such deposits, which are rich in organic materials, become the source rocks for the generation of crude oil. The
process began many millions of years ago with the development of abundant life, and it continues to this day. The
sediments grow thicker and sink into the seafloor under their own weight. As additional deposits pile up, the pressure
on the ones below increases several thousand times, and the temperature rises by several hundred degrees. The mud
and sand harden into shale and sandstone; carbonate precipitates and skeletal shells harden into limestone; and the
remains of the dead organisms are transformed into crude oil and natural gas.
Activity 1: From the above information can you motivate why petroleum which is a natural energy source formed
through natural process can not be uniformly distributed. If not is it randomly? Discus it.
43
Once th
e petroleum forms, it flows upward in Earth’s crust because it has a lower density than the brines that saturate the
interstices of the shales (Shale, common name applied to fine-grained varieties of sedimentary rock formed by the
consolidation of beds of clay or mud), sands, and carbonate rocks that constitute the crust of Earth. The crude oil and
natural gas rise into the microscopic pores of the coarser sediments lying above. Frequently, the rising material
encounters an impermeable shale or dense layer of rock that prevents further migration; the oil has become trapped,
and a reservoir of petroleum is formed. A significant amount of the upward-migrating oil, however, does not
encounter impermeable rock but instead flows out at the surface of Earth or onto the ocean floor. Surface deposits
also include bituminous lakes and escaping natural gas.
V.1.2. Petroleum engineering and petroleum treatment
Petroleum engineering is a special field of chemical engineering that deals with all processes involved during
petroleum treatment from the crude oil up to the final marketable product.
The most important involved processes are:

• Decantation( within purpose of eliminating mud water and other solid matter),
• Degassing(removing several natural gases in crude oil like methane, propane, CO2, …),
• Refining of petroleum by fractional distillation in order to separate different hydrocarbons of petroleum
crude according to their boiling temperature,
• Cracking (process in which heavy hydrocarbons (HH) are converted to lower hydrocarbons (LH)) by
application of heat or a catalyst.
• Reforming (process of heating the gasoline fractional over a catalyst in order to enhance isomerization of
straight chain hydrocarbons to branched hydrocarbon with objectives of reducing the knocking ability and
increasing the volatility, therefore improve gasoline quality.
Note: Crude petroleum is mixture of gaseous, liquid and solid hydrocarbons. It mainly consists of:
(a) Hydrocarbons consisting of alkanes up to 40 carbons, alkenes, cycloalkanes and aromatic
hydrocarbons(like benzene, naphthalene, …)
(b) Impurities derived room nitrogen, sulfur and some fractions of compounds like chlorophyll from plants.
Natural gases consists mainly of methane (84%), ethane (8%), propane (4%), butane (2%) and 2% of
other hydrocarbons.
44
V.2. Refining of petroleum
Petroleum (crude oil) just obtained by mining is viscous and impure with unpleasant smell of sulfur
compounds. The other impurities present include sands and brine or seawater.
Crude oil is first mechanically freed from sand and then subjected to fractional distillation. The process of
converting the crude oil by fractional distillation into useful by- products is called refining of petroleum.
Fractional distillation is done in fractionating tower made of steel. Here the crude oil is first heated in a
furnace to about 4000C and then its vapor is introduced into this tower. As the oil ascends the tower, it will
condense with highly boiling fractions condensing first and low boiling fractions last giving rise to the
following fractions. The following flow sheet of petroleum engineering summarize all process in steps.
Oil Refining and Fractional Distillation

Crude oil is refined into products such as gasoline, asphalt, and waxes by a process called fractional distillation.
During the process, the parts, or fractions, of crude oil are divided out successively by their increasing molecular
weight. For instance, gasoline has a low molecular weight and vaporizes at a fairly low temperature. This means that
at the appropriate temperature, while all of the rest of the oil is still in liquid form, gasoline may be separated out. The
remaining oil goes through the same process at a slightly higher temperature, and jet fuel is divided out. Repeating
the distillation process several times will separate out several constituents of crude oil, which are then processed and
put to a wide range of uses.
Note: Crude oil begins to vaporize at a temperature somewhat less than that required to boil water. Hydrocarbons
with the lowest molecular weight vaporize at the lowest temperatures, whereas successively higher temperatures are
required to distill larger molecules. The first material to be distilled from crude oil is the gasoline fraction, followed
in turn by naphtha and then by kerosene. The residue in the kettle, in the old still refineries, was then treated with
caustic and sulfuric acid, and finally steam distilled thereafter. Lubricants and distillate fuel oils were obtained from
the upper regions and waxes and asphalt from the lower regions of the distillation apparatus.
45
Fractions of fractional distillation of petroleum mixture.
Boiling
Number of
Fraction Temperature Uses
carbon atoms
range
Natural gases C1 – C4 < 30°C fuel
Fuel and
2.Naphta C5 – C15 30-250°C fuel
illumination
(a)Petroleum Fuel and
C5 – C6 30-60ºC
ether solvents
Fuel and
(b)Gasoline C6-C8 70-120°C
illumination
Fuel and
3.Kerosene C10-C15 150-250°C
diesel
4.Light gas Fuel for
oil and diesel C12 – C18 250-400ºC diesel
oil engines
5. Heavy gas
oil , grease
wax, Bitumes and
C17-C40 >400°C
lubrificating lubrification
oil and
vaseline
V.2.1 Purification
After fractional distillation, the gasoline and kerosene fraction are purified by treatment with concentrated sulfuric
acid which removes any aromatic hydrocarbon present as a sulfuric product. Besides treatment with concentrated
H2SO4 various fractions can be purified by passing through an absorbent material like clay containing sometimes
silicon and or slica SiO2.
V.2.2 Cracking
The yield of petrol from fractional distillation is very low. The yield can be improved by heating other fractions in a
process called cracking.
Cracking is therefore, a process in which less volatile higher hydrocarbons are converted to more volatile
hydrocarbons by application of heat or a catalyst.
E.g.: Dodecane present in the light gas oil on heating will break down as below:
46
C7H16 + C5H10
Heat Or
C12H26 C6H14 + C6H12
0
30-150 c
Or C5H12 + C7H14
boiling boiling point
0
point 30 c 1500C
Pt
CH3-(CH2)4-CH3 CH3-CH-(CH2)3-CH3
6000c/300atm
n-heptane 2-methyl hexane
CH3
CH3
Pt
CH3-(CH2)5-CH3
6000c/300atm
n-heptane
Methyl cycloxane
During cracking, the products formed will depend on:
• Structure of the hydrocarbon
• Temperature and pressure applied
Note: The following changes may take place during cracking:
(i) Formation of a mixture of hydrocarbons of lower mass
(ii) Saturated hydrocarbons may be converted to unsaturated hydrocarbons
(iii) Cyclization may occur for instance if hexane from gasoline fraction is heated in the presence of platinum or
Al2O3 catalyst, cyclohexane is formed by the process called reforming.
Pt or Al2O3
CH3-(CH2)4-CH3
6000c
n-hexane
cycloxane
Types of Cracking
There are two types of cracking process used such as thermal c and catalyst cracking.
• Thermal cracking: in this process, the heavier portions of the crude oil were heated under pressure and at
higher temperatures. This resulted in the large hydrocarbon molecules being split into smaller ones, so that
the yield of gasoline from a barrel of crude oil was increased. The efficiency of the process was limited,
however, because at the high temperatures and pressures that were used, a large amount of coke was
deposited in the reactors. This in turn required the use of still higher temperatures and pressures to crack the
crude oil.
• Catalyst cracking: This is done by heating but in the presence of a mixture of silica(SiO2) and Al2O3 or
aluminium silicate as catalyst.
Note: Application of cracking

(i) Manufacturing of petrol. This is done by heating less volatile (high boiling) fraction to form more
volatile(less boiling) fraction.
47
(ii) Preparing o petrol gases. This is done by passing petrol over heated coils.
But, if the gasoline fraction is heated to a temperature of about 6000C at about 3000 atmospheres in the
presence of platinum catalyst, the following change can occur.
(i) Isomerization: i.e. conversion of straight chain alkanes to branched chain isomer
Pt
CH3-(CH2)4-CH3 CH3-CH-(CH2)3-CH3
0
600 c/300atm
n-heptane 2-methyl hexane
CH3
(ii) Cyclisation: Cyclization may occur for instance if hexane from gasoline fraction is heated in the
presence of platinum or Al2O3 catalyst, cyclohexane is formed by the process called reforming.
CH3
Pt
CH3-(CH2)5-CH3
6000c/300atm
n-heptane
Methyl cycloxane
V.2.3. Reforming
Reforming is a process of heating the gasoline fractional over a catalyst in order to enhance isomerization of straight
chain hydrocarbons to branched hydrocarbon with objectives of reducing the knocking ability and increasing the
volatility tendency, therefore improving gasoline quality.
Note:
• Petrol containing straight chain hydrocarbons produce a violet jerking in a car engines causing a metallic
noise in pop-pop so called knocking. This has a negative effect since knocking lowers the efficiency of an
engine and results in loss of energy.
• The quality of fuel is therefore improved by using branched chain hydrocarbons or adding certain
compounds called antiknocks such asTEL(tetraethyl lead: Pb(CH2CH3)4), but nowadays is not used since it
highly contribute to the environment(air) pollution during fuel burning because of lead oxide production
which is very toxic.
• Due to EPA recommendation about selling the gasoline without lead, the above antiknock have been
replaced by Methy tertiobutyl ether(MTBE), tertiobutyl alcohol(TBA)and Ethyl tertiobutyl ether(ETBE).
• In order, to ensure fuel quality, octane number and cetane number, both parameters should be assessed.
• Octane number that measure the ability of a liquid motor fuel such as gasoline to prevent preignition or
knocking. This is expressed as the rating measurement of isooctane (2,2,4-trimethyl pentane, less knocking
for best quality) and n-heptane (more knocking for the worst quality).Fuels with higher numbers are less
likely to cause ignition.
• Cetane number is the measurement of diesel fuel ignition quality. So, it is the performance rating of diesel
fuel expressed as the percentage of cetane in a mixture with 1-methyl naphthalene that shows the ignition
properties. The higher the cetane number, the better the performance.
V. 3. USES of petrol
Apart from petroleum energy issue all over the world, the production of petrochemicals derivatives has given birth to
the gigantic petrochemical industry, which turns out alcohols, detergents, synthetic rubber, glycerin, fertilizers, sulfur,
solvents, and the feed stocks for the manufacture of drugs, nylon, plastics, paints, polyesters, food additives and
supplements, explosives, dyes, and insulating materials. Note that petrol is the dark gold.
48
V.4 Exercises
I. Petroleum, or crude oil, naturally occurring oily, bituminous liquid composed of various organic chemicals.
It is found in large quantities below the surface of Earth and is used as a fuel and as a raw material in the
chemical industry. Modern industrial societies use it primarily to achieve a degree of mobility—on land,
at sea, and in the air—that was barely imaginable less than 100 years ago. In addition, petroleum and its
derivatives are used in the manufacture of medicines and fertilizers, foodstuffs, plastics, building
materials, paints, and cloth and to generate electricity. In fact, its treatment cost highly since it involves
many operation like cracking and reforming.
(i) Explain the meaning of each of the following of terms:
(a) Cracking
(b) Reforming
(ii) What is the importance of cracking in industry and give 2 types of cracking process.
(iii) Explain with motivation why it is not possible in Rwanda to have petrol.
(iv) Develop not in more than 250 words the following statement: “petrol is the dark gold”.
II. The following flow sheet provide different fractions resulting from fractional distillation of petroleum oil:
(i) Identify A
(ii) What is the physical principle or physical properties that allow us to handle this fractional distillation of
petroleum oil.
(iii) Write down the vapor-cracking equation that represent the cracking of a heavy oil containing C16 H34 given
that the two main product are ethene and propene in 1:2 ratio respectively and another hydrocarbon
B.Identify B.
(iv) The laboratory quality control of the kerosene gasoline in order to asses most predominant gases provide a
gas B whose boiling point range about 10-300 C( in fractional distillation of petroleum oil treatment )with
relative density of 1.9 within respect to air but also B contains 85.2% of carbon and 14.8% in hydrogen.
(a) Recognize the possible isomers of gas B
(b) When B is treated with bromine water already red-yellowish, the resulting solution is colorless
but also B gives colorless solution once treated with potassium permanganate (dark purple)
without any gas evolved.
1. Identify B
2. B reacts with bromine water to give a compound C with 22.24% in carbon, 3.71% in
hydrogen and 74.05% in bromine
(i) Write different possible structures of C given that the molar mass of C is
215.8 g.mol-1.
(ii) Among the possible isomers, identify those which exhibit optical properties
in a polarimeter.
(c) In pisido fact, a part from the gas B, a mixture of 3 gases like propyne, ethene and propane
were detected with total volume filled of 50.0Cm3.In order to identify the gases molar fraction,
the mixture produce 125.0 cm3 of a colorless gas that turn milky limewater once burnt with
49
190.0cm3.Give the volume ratio composition and hence deduce from it the percentage of each
gas.
Hint: Molar fraction xi of a compound i in the whole system is given by
Pi P
xi = = ni , therefore
P1 + P2 + P3 + .......... + Pn
∑ Pi
i =1
Vi
= n
where V is volume and P is pressure of a gas i
∑Vi
i =1
50
CHAP VI: ALKYL HALIDES
VI.1.Definition and introduction
Alkyl halide is a class of organic compounds resulting from a simple replacement of one, two or more hydrogen atom(s) in the
structure of hydrocarbons.
Their general formula is R-X where R refer to alkyl group and X to halogens as well as F, Cl, Br, I.
Apart from that they can be classified into primary, secondary and tertiary alkyl halides, as presented below:
H R''
H
R C X R C X
R C X
H R'
R'
tertiary alkyl halide
Primary secondary
H H CH3
H3C C Cl H3C C Cl H3C C Cl
H CH3 CH3
VI.2. Nomenclature and isomerism
• Alkyl halides are named as derivatives of the corresponding alkanes and number is
inserted to denote the position of the halogen atom on the chain.
• In case of many halogen, they are written in alphabetic order while in case of one
halogen present on different position, di ,tri and tetra,… prefix are use and halogen are cited as Chloro, bromo, fluoro,
iodo.
Examples: : CH3I : Iodo methane

CH3-CH2-Cl: Chloro ethane
CH3-CHCl2 : 1,1- dichlore ethane
CH2Cl-CH2Cl : 1,2 –dichloroethane
CCl4: tetrachloromethane
7 6 5 4 3 2 1
CH3 CH2 CH CHBr CH2 CHBr CH3 : 2, 4 - dibromo, 5 - methylheptane
CH3
2-bromo-2-chloro-1,1,1-trifluoro ethane
F3C C Cl
Br
Alkyl halides exhibit both chain and position isomerism
• Position isomerism: This arises due to the different positions taken by the halogen
atom on the same carbon chain and Chain isomerism that arises due to arrangement of carbon atoms in different
chains.
51
Ex. Molecular formula C4H9Br .Let us calculate the deficiency number given by
 0 − (9 + 1) 
i = 4 +1+   = 0, hence there is no double bond or a ring
 2 
CH3-CH2-CH2-CH2Br: 1-Bromo butane CH3CH2-CHBr-CH3: 2-bromo butane
H
CH3
H3C C CH2Br
H3C C Br
CH3
CH3
1-bromo-2-methyl propane
2-Bromo-2-methyl propane
Activity 1: Give all possible structure of CFCs whose molecular formula is C2H2F2Cl2
VI.3.Physical and chemical properties
VI.3.1 Physical properties
1. The first terms of the hydrocarbon series are liquids at room temperature.
2. Their boiling and melting points are high compared to the corresponding
hydrocarbons due to intermolecular forces that increase because attractions are stronger between most
electronegative halogens. But closely, this also take place as molecular weight increase in the same series.
3. They are soluble in water but most soluble in organic solvent as well as fat and oils.
4. They have a characteristic odor and they are more volatile.
5. The relative density of alkyl halides is greater than one what is quite different to
other organic compounds with note to alkyl bromide and iodide for example 2.28 for CH3I and 2.85 for CH3Br.
Activity 2: Explain why most alkyl halides are more volatile.
VI.2.2Chemical properties
Due to the presence of halogen on the hydrocarbon chain, their reactivity is most influenced by halogen, may be to induce
polarity that can lead to nucleophilic substitution (via one or two steps as known as SN2 and SN1 respectively) or elimination.
Nucleophilic substitution reaction:
R X + Nu- R Nu + X -
Nucleophile
(a) Reaction with aqueous alkali: when alkyl halides are refluxed with aqueous alkali, or moist silver oxide, alcohols
are produced. CH 3 − CHBr − CH 2 − CH 3 + OH − →
Dilute KOH
CH 3 − CHOH − CH 2 − CH 3 + Br −
e.g. CH 3 − CH 2 Br + KOH → CH 3CH 2OH + KBr
waerm
Warm
R X + AgOH R OH + AgX
52
OH
Cl
H3C C CH3 + KOH H 3C C CH3

+ NaCl
Warm
CH3 CH3
Note: Tertiary alkyl halides react by SN1 mechanism because the first step is the self ionization forming a carbanium
ion in which immediately adds the nucleophile.
Secondary alkyl halides however react by either SN1 or SN2 mechanism depending on the condition of the
reaction while primary alkyl halides react by SN2 du steric hindrance
SN1: Unimolecular Nucleophilic Substitution that takes place in two steps.
SN2: Bimolecular Nucleophilic Substitution that takes place in one steps.
• The order of reactivity for same alkyl group is such that iodides>bromides>chlorides.
EX: CH3-I reacts faster than CH3-Br which also react faster than CH3-Cl
Halogen atoms being more electronegative than carbon atom pull electrons more towards themselves and this creates partial
charges on carbon and the halogen atom.
The greater the electronegativity, the greater the separation of charges on the carbon and the halogen atom, hence the stronger
the bond. Therefore reaction is fastest with Iodoalkane because iodine is less electronegative copmpared to Brand Cl. hence it
will have weak C-In bond unlike that of C-Cl which will be very strong due to the strong electronegativity of the chlorine
atom . Hence bond energies below are due to the above reason.
Type of bonds C-I C-Br C-Cl
Bond energy (kCal) 43.5 54 66.5
Because the carbon atom attached to the halogen atom is deprived of its electron, it carries a partial positive charge
− C ∂ + − X ∂− . Thus when electron rich substrates called nucleophiles, approach the carbon atom, the halide atom
leaves as a halide ion . Hence alkyl halides undergo nucleophilic substitution reaction.
(b) Reaction with sodium alkoxides

Treatment of alkyl halides with sodium alkoxides produces ethers (Wiliamson synthesis)
R − X + R − O − Na heat
→ R − O − R + NaX
CH 3CH 2 − Br + CH 3 − CH 2 − O − Na + heat
→ CH 3 − CH 2 − O − CH 2 − CH 3 + NaBr
C. Reactions with silver salt of carboxylic acid
When alkyl halides are refluxed with silver salt of carboxylic acid esters are formed.
R − X + R ' COO − Ag + heat
→ R − O − CO − R '+ AgX
e.g : CH 3CH 2Cl + CH 3CH 2COO − Ag + → CH 3CH 2O − CO − CH 2CH 3
heat
Silver propanoate ethyl propanoate
d. Reaction with potassium cyanide

When alkylhalides are refluxed with KCN, in presence of an alcohol, alkyl nitriles are produced
R − X + KCN 
heat / alcohol
→ R − C ≡ N + KX
e.g : CH 3 − CH 2 − CH 2 − Cl + KCN 
Heat alcohol
→ CH 3 − CH 2 − CH 2 − CN + KCl
butanonitrile
Note: This reaction is of practical importance in organic synthesis in that it is used to increase the length of a carbon chain.
e. Reaction with silver nitrite

When alkyl halides are refluxed with silver nitrite, a mixture of a nitro alkane and alkyl nitrite are obtained as the
products.The two products can be separated by fractional distillation.
53
CH 3 − O − N = O methyl nitrite

CH 3 − Br + AgNO 2 heat
→
 
CH 3 NO 2 nitromethane
f. Reaction with ammonia and the amines

Reaction of alkyl halide with concentrated ammonia produces a mixture of amines.
R-CH2-I + NH3 → R-CH2-NH2 + HI
The alkyl amine produced can then react with a fresh molecule of alkyl iodide.
CH 3 − CH 2 − I + CH 3 − CH 2 NH 2 → (CH 3 − CH 2 ) 2 NH + HI
Diethyl amine
(CH 3 − CH 2 ) 2 NH + CH 3 − CH 2 − I → (CH 3 − CH 2 ) 3 N + HI
Triethyl amine
(CH 3 − CH 2 ) 3 N + CH 3 − CH 2 − I → (CH 3 − CH 2 ) 4 N + HI −
Tetra ethyl ammonium iodide
Summary of alkyl halides reactions

nucleophilic reagents Products
OH- (Base) R-OH
R’-O- (R’-O-Na) R’-O-R (ether oxyde)
RCOO- (RCOONa) RCOOR’ :ester
CN- (KCN) R-CN (nitrile)
R’C ≡ C
− R’-C ≡ C − R
R- (RMgX) R’-R
NO2- (AgNO2) R-NO2
2. Elimination reaction
Alkyl halides when boiled with alcoholic potassium hydroxide form alkenes by elimination reaction. Hence the alkyl
halide loses a molecule of the halogen acid.
Ex : CH3-CHCl-CH3 + KOH  → CH 3 − CH = CH 2 + KCl + H 2 O

Alcohol
Note: Elimination reaction usually occurs in competition with substitution reaction. So when chloromethane is
refluxed with a solution of potassium hydroxide in ethanol two products are formed.
Ethene is formed by elimination reaction while diethyl ether is formed by substitution reaction.
Mechanism: Ether is formed by SN2 mechanism in which CH3CH2O- is acting as nucleophile.
While Ethene is formed by elimination reaction is which CH3CH2O- is acting as base.

_ _
+
CH3CH2OH + CH2=CH2 Cl
_
CH3CH2O + CH2-CH2 Cl
H
In the mechanism for the formation of Ethene, the reagent present at the transition state is
CH3CH2-O……...CH2,,,,,,,,,,,,,, CH2……..Cl where the O-H and C=C are partially formed while C-H and C-Cl are
partially broken.
Because the two molecules are involved i.e CH3CH2O- and CH3CH2Cl the reaction is bimolecular and since the alkyl
halide loses a mole of HCl the reaction is called elimination. Hence reaction is E2.
In competition between SN2 and E2 in primary or secondary alkyl halides, the nature of the product formed depends
on the solvent, temperature, and structure of the halide.
54
Elimination is favored by use of high temperature and a strong base e.g alcohol instead of water.
For tertiary alkyl halides, elimination occurs by E1 mechanism. In the mechanism, the tertiary alkyl halide undergoes
ionization first and then later loses a proton.
Br
hot KOH
H3C C CH2
H3C C CH3 Ethanol + KBr + H2O
CH3
CH3
3. Wurtz reaction
Alkyl halides with sodium metal to give alkanes.
2CH 3CH 2 Br + 2 Na ether
 → CH 3 − CH 2 − CH 2 − CH 3 + 2 NaBr
/ heat
4. Reaction of poly halides
These are compounds in which more than one halogen atom is present. There are two types of poly halides.
Gem dihalides: This is where two halogen atoms are attached to the same carbon atom.
e.g.
CH 3 − CCl2 − CH 3
Vicinal dihalides: Here the two halogen atoms are adjacent carbon atoms. e.g. CH 3 − CH 2 − CHCl − CH 2Cl
Reactions
Similar to those of mono alkyl halides but required more reagents.

CH 3 − CH − CH 2 + 2 NaOH aq → CH 3 − CHOH − CH 2OH + 2 NaCl
heat
| |
Cl Cl
CH 3 − CHCl − CH 2Cl + 2 KCN   → CH 3 − CH − CH 2 + 2 KCl
alcohol / heat
| |
C≡N C≡N
Elimination reaction with excess hot alkali produces alkynes
CH 3 − CH 2 − CHCl2 excess
 hot  → CH 3 − C ≡ CH
/alcolic KOH
CH 3 − CCl2 − CH 3 excess
 hot  → CH 3 − C ≡ CH
/alcolic KOH
V.4 Preparation of alkyl halides

1. From alkenes
Addition of halogen acid (HX) to alkenes gives alkyl halides as the products. The orientation in the addition reaction is
described by Markovnikov’s rule (see alkenes).
X
C C
H2SO4
C C + HX H
C C
X
2. From alkanes
Direct halogenation of alkanes in the presence of ultraviolet light gives alkyl halides
R − H + X 2 →
UV
R − X + HX
3. From alcohols
The hydroxyl (-OH) of alcohols is replaced by reaction with halogen acids, phosphrous halide or thionylhalides.
55
* ROH + HX → RX + H 2 O
* 3ROH + PBr3 → 3RBr + P(OH ) 3
* ROH + PCl 5 → RCl + HCl + POCl 3

* ROH + SOCl 2 → RCl + SO2 + HCl
Activity 2 : Using the explanatory mechanism, motivate the above results.
4. From aldehydes or ketones

Cl
O
PCl5 + O=PCl3
R C R'
R R'
Cl
5. From alkynes: R − C ≡ C − R'+2 HX → R − CH 2 − CX 2 − R'
VI.5 Alkyl halides uses
Alkyl halides have many uses in our every day life such as in agriculture, industry as solvents, medicine and
in pharmacy.
Solvents:
• CH2Cl2 in varnish and paints manufacturing
• CCl4 is used as the most organic solvent for fats and oils and can be used as fire extinguisher
• CH3CCl3: is used in cleaning of most ink.
• CHCl=CCl2: is used in dry cleaning and in caffeine extraction
• CFCs: chlofluorocarbons
Medicine:
• CHCl3 (chloroform): is used in anesthesia
Agriculture:
• DDT: Dichloro diphenyl trichloroethane is used as insecticides DDT, colorless chemical pesticide,
dichlorodiphenyltrichloroethane, used to eradicate disease-carrying and crop-eating insects. It was
first isolated in Germany in 1874, but not until 1939 did the Swiss Nobel Prize-winning chemist
Paul Müller recognize it as a potent nerve poison on insects.
Cl CH Cl
CCl3
However, with the publication of the American marine biologist Rachel Carson's Silent Spring in 1962, suspicion
grew that DDT, by entering the food chain and eventually concentrating in higher animals, caused reproductive
dysfunctions, such as thin eggshells in some birds. Some insect pests also gradually developed DDT-resistant strains
whose populations grew unchecked while their natural predators, such as wasps, were being eradicated by spraying.
In 1973 DDT was banned in the U.S. except for use in extreme health emergencies. Many other nations have also
banned it or placed it under strict control.
56
• HCH: HexaChlorocyclohexane
Cl
Cl
Cl
Cl
Cl
Cl
• Dieldrine and enderdrine as termites’ killer in order to protect eucalyptus.
Plastics:
• Polyviny chloride(PVC): PVC is the most widely used of the amorphous plastics.
PVC is lightweight, durable, and waterproof. Chlorine atoms bonded to the carbon backbone of its
molecules give PVC its hard and flame-resistant properties.
In its rigid form, PVC is weather-resistant and is extruded into pipe, house siding, and gutters. Rigid PVC is also
blow molded into clear bottles and is used to form other consumer products, including compact discs and computer
casings.
PVC can be softened with certain chemicals. This softened form of PVC is used to make shrink-wrap, food
packaging, rainwear, shoe soles, shampoo containers, floor tile, gloves, upholstery, and other products. Most softened
PVC plastic products are manufactured by extrusion, injection molding, or casting.
• CF2CF2: form polymers that are used in orthopedic and prosthetic appliances, hearing
aids, corrosion resistant and mechanical parts, upholstery, joints, flying pan coatings, electric insulation.
Activity 3: Discus the uses and inconvenient of CFCs.
VI.6. EXERCISES
I. Complete the following chemical reactions and determine their functional groups for
products:
1.CH2=CH-CH2-CH2-CH2Br + KOH
2. CH2=CH-CH2Br + HBr
3. CH3-CHOH-CH3 + PBr3
4. CH3-CHCl-CH3 + CH3CH2ONa
5.CH3-CH(CH3)-CH2I + HCOONa
6.Br-CH2-CH2-CN + KCN
7. CH2=CCl-CH2CH3 + KOH(dilute)
II. How can you effect the transformation of CH2=CH-CHBr-CH3 in one or more steps :
a) CH3-CHOH-CHBr-CH3
b) CH3-CHOH-CHOH-CH3
c) CH2=CH-CHOH-CH3
57
III. How can you prepare 2-Bromo pentane from:

a) Pent-2-yne
b) HOCH2-(CH2)3-CH3
c) 1-Bromopentane
d) 1,2-Dibromopentane
e) CH3-CHOH-CH2-CH2-CH3
IV. Indicate the series of reactions that can use to perform the following test <<from
………to>>.
a) From 1-chloro pentane to 2-chloro pentane
b) From 1-chloro pentane to pent-1-yne
c) From 1-chloro pentane to CH3CH2CH2CHO
d) From 1,2,2-Trichloro ethylene to hexacholoro ethane
e) From CH3-CHOH-CH3 to CH3-CH(NH2)-CH3
f) From ethyne to 1,1-dicloro ethane
g) From CH3-CO-CH3 to 2,2-dicloro propane
V. What are the effects of Chloro triphenyl methane as known as trityl chloride used as
insecticide with the following formula :
Cl
VI. Try to replace each letter by the corresponding organic molecule and try to recognize
its functional group.
H2SO4
2Na
1. A + H2O B PCl5 C 3,3,4,4 tetramethyl hexane
CH3ONa
D
2. C2H2 + NaNH2 A + NH3
A + isopropyl bromide B + NaBr
B +H O Hg2+ C
2
C + PCl5 D + POCl3
VII. Most air pollutants in our environment includes the so called CFC.
(i) What is the meaning of CFC
(ii) Among available CFC, one is well recognized has the following molecular formula
C2HF3Cl2
• Give all possible structure whose the above molecular formula and define their
relationship.
58
(iii) Give the uses of CFC

(iv) State the environmental effect of CFC and try to suggest the remediation against
these negative impacts above mentioned.
INDEX NOTE
Isomerism
Isomerism is the existence of compounds with same molecular formula but different structural formulae. The compounds are
called isomers. There are two types of isomerism:
1. Structural isomerism and
2. Stereoisomerism
1. Structural isomerism
This type of isomerism arises from the differences in the arrangement of atoms within the molecule resulting in two or more
different structural formulae. Thus structural isomers have same molecular formula but different structures. Structural
isomerism is further subdivided into:
(a) Chain isomerism: This type of isomerism is due to the difference in the structure of carbon chain or the arrangement of
carbon atoms in the molecule
e.g. C5H12
n-pentane : CH2 CH2
H3C CH2 CH3
H3C CH2
isopentane :
CH CH3
CH3
H3C
CH3
neopentane: C
H3C
CH3
b)Position isomerism : In compounds containing similar carbon chain (homologous series ), the difference in
positions occupied by a particular atom or subsitutient in the carbon chain gives rise to position isomerism.
H3C CH2 CH3
H3C CH2 CH2OH CH2 CH
CH2 CH2 HO
e.g. 1) And
2)
H3C CH H3C CH
CH CH3 CH2 CH2
and
c) Functional isomerism
This is isomerism where the isomers differ in the functional groups. Since the
Property of a compound is largely determined by functional groups, such compounds differ in their physical and
chemical properties.
E.g.
59
H3C CH2 OH H3C O CH3

and
H3C CH CH2 CHO

H3C CH2 CH2 COOH OH
and
2. Stereoisomerism
Stereoisomerism occurs when two compounds have the same molecular formula and same structural formula but
differ in the spatial arrangement of atoms. Stereoisomerism is further sub divided into
(a) Geometrical isomerism

(b) Optical isomerism
(a) Geometrical isomerism
In geometrical isomerism, the isomers have same structural formula but differ in spatial arrangement of the groups
around the double bond. The isomer with similar groups on the same side of the double bond is called Cis isomer
while that with the same group on the opposite is called a trans isomer.
Exemple1) 1,4 butenedioic acid C4H4O4
HOOC COOH HOOC H
C C C C
H H And H COOH
Table3:Physical parameters of maleic and fumaric acid

Cis but-2-enedioic acid Trans1,4 but-2-enedioic acid(
FOCUSED PARAMETER
(maleic acid) fumaric acid)
130°C Melting points 302°C
79 Solubility (g/100 g H2O) 0,7
1000 Ka1 96
Example 2:
CH3 H3C H
H3 C
C C
C C
H CH3
H H
cis - 2 - butène trans - 2 - butène
Ph COOH Ph H
H H H COOH
cis trans
Note 1: For a compound to be a geometrical isomer, the 2v similar groups should not be on the same carbon atom.
Therefore, it is not a geometrical isomer.
Note 2. E – Z Convention
Sometimes Cis – Trans is not sufficient in case of 4 different substituents. Therefore E-Z can be used
instead of Cis – Trans.
F Br
Cl I
is it Cis or Trans
60
The prefix E (from German: entgegen = opposite)
The prefix Z (zusammen = same side)
Examples:
F Br 2
1
H3CH2C CH3
H3 C Br
Cl I
2 1
Z-1-Bromo-2-Chloro
2-Fluoro-1-Iodo ethene E-2-Bromo-3-Methyl but-2-ene
(b) Optical isomerism
Optical isomerism arises when two compounds have same molecular and structural formulae, but one is not super
imposable upon the other. The 2 compounds differ in the way they rotate plane-polarized light.
This property where a compound rotates plane-polarized light is called optical activity. Whereas geometrical isomers
may show marked difference in their physical and chemical properties, optical isomers have similar physical and
chemical properties except that they show pronounced difference towards plane-polarized light.
mirror
CHO CHO
H OH HO H
CH2OH CH2OH
D-(+)Glyceraldehyde L-(-)Glyceraldehyde
a a
C* d d C*
b b
c c
Enantiomer pairs or antipodes
Note: For a compound to show optical isomerism, the molecule should be asymmetric i.e. the carbon atom at the
middle should be attached to 4 different groups.
Optical isomers are also possible as much as the substitution of hydrogen atom increase for example lactic acid which
exists in two isomers that are mirror images of each other, yet they cannot be superimposed on each other since that
molecule has an asymmetric carbon and do not have any symmetric element like centers, axes and planes.
Just as the right hand and left hand are different, optical isomers (known as enantiomers) are different from each
other and can have different properties. For example, muscles produce D-lactic acid when they contract, and a high
amount of this compound in muscles causes muscular pain and cramps.
On the other hand, sour milk contains L-lactic acid, giving the milk its sour taste.
61
These molecules optical isomers, because the molecules of one isomer will rotate the direction of a beam of plane-
polarized light (light that is traveling in the same plane, not in all directions) in the opposite direction that the other
isomer will.
Enantiomers are often identified with a D- or L- prefix because of the direction they rotate polarized light.
Enantiomers that rotate polarized light in a clockwise direction are known as dextrorotatory (right-handed)
molecules, and enantiomers that rotate polarized light in a counterclockwise direction are known as levorotatory
(left-handed) molecules.
• A solution containing equal amounts of both enantiomers ( 50% levorotatory and 50% dextrorotatory is
known as a racemic mixture that will not rotate polarized light, because the rotations of the two
enantiomers cancel each other out.
Examples:
* *
H3C CH2 CH CH3 H3C CH CH2OH
*
OH NH2 OH
Activity 4: Give all optical isomers of taritric acid (HOOC-CHOH-CHOH-COOH) and determine whether are
enantiomers that can rotate the polarized light in left or right direction. Give the exact name.
62
CHAPVII: ALCOHOLS
VII.1 Introduction
Alcohols are organic compounds that are derivatives of hydrocarbons where one or more hydrogen atoms of
hydrocarbon is or are replaced by hydroxyl (-OH) group. They are represented by the general formula:
CnH2n+1 –OH or R-OH where R is a radical: alkyl and aryl (phenyl).
Alcohols are called monohydric if only one hydroxyl group is present (eg : CH3CH2-OH)
Dihydric alcohols are those with two hydroxyl group (diol: vicinal and gem), trihydric (triols) and polyhydric are
those with many –OH groups. The functional group attached is –OH group to a any atom of carbon.
Hence, monohydric alcohols are classified as:
i. Primary alcohol: These have only one alky group attached to the carbon carrying the –OH i.e R-OH
example CH3OH, CH3-CH2-CH2-CH2-OH.
ii. Secondary alcohols: these have two alkyl groups attached to the carbon of the –OH group.
R H H
HO C R
' HO C CH3 HO C CH2CH3
H For example: CH3 CH3
OH
OH or both are cyclic alcohols
iii. Tertiary alcohols: these have three alkyl groups.
OH
R
CH3
OH
HO C ' HO C CH3 phenol
R
R'' for example: CH3
VII.2 Nomenclature and isomers
According to IUPAC system, alcohols are named by replacing the final<<e>> of the parent hydrocarbon
with<< ol >>, then specify the position of OH group before ending by ol.
Examples: CH3OH: Methanol
CH3-CH2-OH: ethanol
CH3-CH2-CH2-OH: Propan-1-ol and CH3-CHOH-CH3: Propan-2-ol
H
HO C : butan-2-ol
CH2CH3
CH3 ;CH3-CH2-CH2-CH2OH: Butan-1-ol
OH
CH3
HO C CH3 :2-methyl propan-2-ol or Cyclohexanol

tertiobutanol
CH3
HOCH2-CH2OH: Ethane-1, 2-diol commonly known as ethylene glycol used as antifreeze in
some radiator of vehicles in the rain season in European country.
HOCH2-CHOH-CH2OH: propane-1, 2, 3-triol commonly known as glycerin or glycerol.
CH3-CH=CH-CHOH-CH2-CHCl-CH3: 6-Chloro hept-2-en-3-ol
(CH3)2 CH-CHOH-CCH: 4-Methyl pent-1-yn-3-ol
63
Notice:
i. OH group take priority over alkyls substituents, double or triple bonds and even
halides. But in case of cyclic compounds with double linking alcohol can be
taken as hydroxyl substituent. Let us consider the following example to make
clear these exceptions.
OH
: phenyl methanol
HO CH2 CH2 OH
1,4-(dihydroxy dimethyl)-cyclohexane
Regarding the issue of isomerism, we have :

• chain isomers: this is due to the difference in the structure of the chain for example: butan-1-ol
and 2-methyl propan-1-ol or 2-methyl propan-2-ol),
• Position isomers: this is due to different positions taken by the –OH in the same carbon chain
and leads to three class of monohydric alcohols as above discussed (e.g.: for C3H8O: there exist
propan-1-ol and propan-2-ol while for C4H10O has 4 position isomers such as butan-1-ol, butan-
2-ol, 2-methyl propan-1-ol and 2-methyl propan-1-ol).
• Functional isomers: Except methanol which has one carbon, other alcohols are isomers with
ethers another chemical function of general formula R-O-R’ where R and R’ are alkyl groups or
aryl groups but not hydrogen.
E.g: C2H6O has 2 functional isomers: CH3-CH2-OH (Alcohol: ethanol) and CH3-O-CH3 (ether:
methoxymethane or dimethyl ether).
C3H8O represents CH3CH2CH2OH or CH3 -CHOH-CH3 (both alcohols) and one ether: CH3-CH2-
O-CH3 (methoxymethane).
VII.3 Physical and chemical properties
VII.3.1Physical properties
The most properties of alcohols result to the presence of OH group while R has no significant effect
even though it influence in some cases.
(i)The lower members are generally liquids up to C5H11-OH while the higher ones are solids due
to the presence of hydrogen bonding that enhance intermolecular force thereby leading to high
attraction which held strongly the molecular structure.
(ii) They have a characteristic sweet alcoholic smell that can be appreciated or not.
(iii) Alcohols have relatively higher boiling points compared with hydrocarbons of
approximately the same molecular mass and the same carbon number because of formation of
hydrogen bonds which is not possible with hydrocarbons but also strong hydrogen bonding that
lead to high intermolecular forces which require high energy to be broken down and hence the
boiling point increase as the number of OH increase
R
R
O
H
H O H
R CH2-O HOCH2
R
O HYDROGEN
R BONDING
H
64
Let us consider the following table:

Molecule Molec Boiling point in 0C
ular
mass
CH3-CH3(Ethane) 30 -42
CH3OH(Methanol) 32 46
CH3CH2OH 46 78
CH3CH2Br 109 38
CH3CH2CH2OH 60 98
CH4 15 -182.6
HO-CH2-CH2-OH(Ethane-1,2diol) 62 192
HOCH2-CHOH-CH2OH(Glycerin) 90 290
(iv)Alcohols form azeotrope with water

(v) The lower members are readily soluble in water but solubility decreases with molecular mass
i.e as the length of the carbon chain increase.
Their solubility in water is due to the formation of hydrogen bond between highly polarized –OH
groups and water molecule. Merely, the higher alcohols become less soluble because of the
increase in the length of the water insoluble hydrocarbon chain.
hydrophilicH
pater soluble H
in water
R CH2 CH2 O H-O
O
water
Hydophobic pole insoluble in water
hydrogen bonding
between alcohols
and water
(Vi) Alcohols are less volatiles than other alkyl halides and some can have the considerable
viscosity as their OH group increase such case of glycerin and propan-1-ol; this is due to the
presence of many OH groups in glycerin that have intramolecular forces which are more stronger
than intermolecular forces that enhance the cohesion and hence the viscosity increase while his
homologue propan-1-ol is a liquid that is volatiles almost ethanol since the interaction becomes
considerable in polyhydric alcohol.
VII.3.2 CHEMCAL PROPERTIES
The molecule of an alcohol consists of an alkyl group and functional –OH group. The C-O bond
and O-H are both polarized with oxygen atom carrying a partially charge and yet it has unshared
pair of electrons.
The reaction of alcohols therefore consists of;
a. The cleavage of C-O resulting in either nucleophilic substitution or elimination.
b. Cleavage of O-H bond resulting in substitution of hydrogen.
c. Oxidation of carbon atom carrying O-H group for primary and secondary alcohol to give carbonyl
derivatives: aldehydes (late carboxylic acids) and ketones respectively except tertiary alcohols that
do not undergo oxidation.
1.1.1 Reaction involving the cleavage of O-H

a. Action of electropositive metals
Electropositive metals like Na, K, reacts with alcohols forming alkaoxide with evolution
of hydrogen gas that produce pop- motion.
65
2 R-OH + 2 Na 2 R-O-Na + H2(g)

Alcolate
Notice: (a) In this reaction, alcohols are behaving as weak acids since they do not easily release the proton
from O-H because Oxygen is more electronegative than H of OH, thus it attracts strongly Hydrogen, and
therefore H can not be freely liberated.
R-OH + H2O R-O- + H3O+
Acide
(b) Alcohols also behave as weak bases by reaction with mineral acids.
R-OH + H2O R-OH2+ + HO-
BASE
R-OH + Na +NH2- R-O-Na +NH3

Hence, alcohols are amphoteric species since they are neither acidic nor basic enough to affect litmus paper reason
why more generally described as neutral.
b. Esterification
Alcohols react with organic acids in the presence of mineral acids like sulfuric acid (as catalyst) with
elimination of water under 1000C to produce an ester with given off a perfume smell. This reaction is called
H 2S O
R ,- O H + R -C O O H
4
R -C O O R , + H 2O
1 0 0 0C E s te r
R '- O H + R -C Cl
R -C O O R , + H C l
, R -C O O R , + R -C O O H
esterification. R - O H + R -C O O R
c. Alkylation reaction and etherification
Alcohols react with dialkylsulphate by replacement of the hydrogen of the group by an alkyl group forming
ether and alkyl derivatives, the same two alcohols react to give ether or an alcolate reacts with alkyl halides.
R'-OH + R2 SO4 R-OR, +R, HSO4
dialkyl sulphate ether alkyl hydrogen
sulphate
R-OH + R’-OH 
H 2 SO4 ∆
→ R-O-R’+ H2O
CH3CH2-OH + CH3OH  H 2 SO4 ∆
→ CH3CH2 -O-CH3 + H2O
1.2 Reaction involving the cleaving of C-O bond
(a) Action of halogen acids(HX)

Alcohols reactions also considered as those in which the –OH group is totally replaced during substitution
(SN2).
(i) Action of halogen acids (HX)
Alcohols react with halogen acids to give alkyl halides.
CH3CH2CH2CH2-OH + HBr CH3CH2CH2CH2-Br + H2 O
H Cl
HCl/ZnCl2
HO C : butan-2-ol CH3CH2 CH
CH2CH3
CH 3
CH3
66
CH3
CH3
HO
HCl/ZnCl2
C CH3 :2-meth yl p ropan-2-ol or CH3-C-CH3
tertiob utano l
CH3
Cl
Notice: (i) Reaction with concentrated hydrochloric acid is catalyzed by anhydrous zinc chloride.
(ii) This reaction is called LUCAS test and is used to distinguish between simple primary, secondary or
tertiary alcohols. In this reaction, the alcohol is shaken with a solution of zinc chloride in
concentrated hydrochloric acid.
Observations: Immediate cloudiness indicates presence of a tertiary alcohol. If the solution becomes
cloudy within 5 minutes then the alcohol is a secondary one. Primary alcohol would show no cloudiness
at room temperature since the reaction is very slow. For example all alcohols are isomers in their class of
C4H10O can be distinguished by this test of LUCAS.
This reaction respects nucleophilic substitution mechanism in two steps (SN1) via carbocations for tertiary
alcohols while primary alcohols respect SN2.
• Reactions occur fastest with tertiary alcohols because a tertiary carbanium is formed fastest and is
more stable since donatives group increase the stability.
b. Action of nitric acid on alcohols.

ROH + HNO3 R-O-NO2 +H2O
C. Action of phosphorus halides
Alcohols react with phosphorus tri and pentahalides to form alkyl halides
3 R-OH + PCl3 3 R-Cl + H3PO3
R-OH + PCl5 R-Cl + O=PCl3 + HCl
Similar reaction occurs with PBr3, PBr5, PI3 and PI5. In these reactions HCl gas evolved suggest the
presence of –O-H group.
d. Action of thionyl halide

Alcohol react with thionyl chloride or bromide to form alkyl halide (chloride or bromide) respectively.
R-OH + SOCl2 R-Cl + SO2 + HCl

CH3 CH3
OH Cl
H
SOCl2/pyridine or Et3N H
+ SO2 + HCl
Notice: This reaction generates the green house gas (that may cause green house effect and acid rain
deposition) SO2 confirmed by the acidified dichromate paper which turns from orange to green due to
oxidoreduction reaction.
2. Reaction with sulfuric acid
Alcohols react with concentrated acid to give products depending on the nature of the alcohol and conditions
of reactions.
(a) At about 00C alcohols react with sulfuric acid to produce alkyl hydrogen sulphates.
(b) At about 1400C in the presence of excess primary alcohol and concentrated sulfuric acid, an ether is
formed.
H2SO4 /1400C
2R-CH2OH R-CH2-O-CH2-R + H2O
67
M e c h a n is m :
H 2S O 4 H + + -O S O 3 H + H
C H 3C H 2 O H + H+ C H 3C H 2 O
H
+ H
C H 3C H 2 O + C H 3C H 2-O H C H 3C H 2-O C H 2C H 3 + H 2O
H
(c) Elimination reaction

Alcohols are dehydrated by heating with concentrated sulfuric acid or phosphoric acid to alkenes.
The ease of dehydration is in the order tertiary>secondary>primary.
H2SO4 CH3-CH=CH2 + H2O
CH3-CH2-CH2-OH 0
170 C
Notice: For primary alcohols any temperatures between 1500C-1800C is sufficient and the acid should be
sufficiently concentrated.
OH
Conc H3PO4
Heating 1600C
2-Phenyl ethanol STYRENE

Notice: This dehydration respects Zaïtsev’s elimination law( see alkenes) reason why the hydration of butan-
1-ol and butan-2-ol gives the same products which is but-2-ene via E1 catalyzed by concentrated H2SO4.
• Elimination always competes with nucleophilic substitution reaction. Substitution leading to
formation of ether is favored by use of excess primary alcohols while higher temperatures favor
elimination. Therefore, dehydration of ethanol may produce both alkenes by elimination and diether
by substitution reaction. The relative proportion of two products depends on the condition of the
reaction.
H2SO4/High temperature
CH2=CH2
CH3-CH2OH
H2SO4/low temperature
CH3CH2-O-CH2CH3
(iii) Dehydration of alcohols also occurs when the vapors of the alcohols are passed over heat aluminium
oxide at about 3000C.
Al2 O3
CH3-CH2OH(g) CH2=CH2
3000C
OH
Al2 O3
High temperature
3.2.3 Reaction of oxidation: Reaction involving C carrying –OH
Primary and secondary alcohols are oxidized to aldehydes and ketones respectively by use of acidified
K2Cr2O7, CrO3, KMnO4 acidified, nitric acid once concentrated.
68
O
C r 2 O 7 2 - /H + C r 2 O 7 2 - /H +
R -C H 2 O H R -C R -C O O H
H e a tin g
p rim a ry H e a tin g H A C ID
a lc o h o l AA LD EH YDE
C r 2 O 7 2 - /H +
R -C H O H -R R -C O -R '
II n d a lc o h o l R'
H e a tin g K e to n e
C r 2 O 7 2 - /H +
R C R
'' n o re a c tio n
H e a tin g
O oHh o ls
te rtia ry a lc
Notice:
1. Tertiary alcohols resist to oxidation
2. Aldehydes formed by oxidation of primary alcohols tend to undergo further oxidation to carboxylic
acid.
3. Oxidation also occurs when the alcohol is in gaseous phases by used of silver or copper catalyst
under 5000C and 3000C respectively; and the vapor of the alcohol is passed with air(oxygen) over
heated silver.
4. This reaction allows us to distinguish primary, secondary alcohols with tertiary alcohols because a
primary and secondary alcohol colorless the solution of KMnO4 from violet while the acidified
potassium dichromate is turned from orange to green. This is the general principle of breathalyzer
(a trademark for an apparatus that measures a subject's blood alcohol concentration from his or her
breath) used by the police to test whether the driver is drunkard or not.
5. Secondary alcohols having the following structure R-CHOH-CH3 only undergo oxidation, on
treatment with iodine solution in the presence of sodium hydroxide to give yellow precipitate of tri-
iodomethane.
Note: This is a reaction which is characteristic of methyl ketones, CH3-CO-R’; but iodine here acting as an
oxidizing agent first oxidizes the CH3-CHOH-R’toCH3-CO-R’ ; then the methyl ketone formed then gives the
yellow precipitate of CHI3 (Iodoform). From the reaction involved we have the Iodoform test.
O
H
+5N aI
R C CH3 + 6 N a O H + 4 I2 C H I 3 + R -C ONa
+
OH W a rm 5H 2O
Activity: How can distinguish:

1. Methanol and ethanol
2. Propan-2-ol and pentan-2-ol
3. Butan-2-ol and 2-methyl pentan-2-ol
4. Ethanol and butan-1-ol
5. Phenol and methanol.
VII. 4. Alcohol preparations
(a) From alkyl halides

Alkyl halides when refluxed with aqueous alkali( NaOH or KOH) or moist silver oxide (AgOH) produce
alcohols. The hydrolysis occurs by a nucleophilic substitution reaction.
69
warm OH
R-X + KOH R-OH + KX
+ K+OH
Br warm
- + KBr
I OH
Warm
CH3CH2 C CH2CH3 + AgOH CH3CH2 C CH2CH3
-AgI
CH3 CH3
Yellow
precipitate
Note: During the reaction of these preparations of alcohols, you have to use the dilute NaOH, KOH under
warm condition in order to increase the rate of SN2 for primary alcohol while tertiary alcohols undergo SN1.
(b) From alkenes
(a) Alkenes react with concentrated H2SO4 to form alkyl hydrogen sulfates by electrophonic
addition. These alky hydrogen sulfates on hydrolysis with water or steam from alcohols by
nucleophilic substitution reaction. Or more simply the action water on alkenes respects
Markovnikov law.
H2O R-CHOH-CH3
R-CH=CH2
H2SO4
CH3CH=CH2 H2O CH3CHOH-CH3
H2SO4
OH
H2O
H2SO4
Notice: Alkenes in the presence of aluminium oxide reacts with water to form alcohols in vapor phase then
condense to give liquid alcohols.
OH
CH3
H2O
CH2 CH3 C CH3
CH3 C
Al2 O3
CH3
• The action of dilute KMnO4 on alkenes allow us to produce diol through Syn hydroxylation
R''' R Dilute KMnO4 R''' R
R'' R'
Warm
R' OH OH
R''
Viccinal
diol
OH
dilute KMnO4
Warm OH
Cis cyclohexane-1,2-diol
3. From carbonyl compounds

When aldehydes and ketones are reduced in the presence of suitable catalyst like Pt, Ni or Pd, they form
primary and secondary alcohols respectively.
O
H2/ Pt
R C R CH2OH
H
O R,
H2/ Pt
R C R CHOH
R,
70
Ni
CH3CHO + H2 CH3CH 2OH
HEAT
CHO CH2OH
H2/Ni
HEAT
O OH
H2/Pt
Heat
Note: 1.Lithium aluminium anhydride can also be used as a reducing agent.

LiAlH4
CH3CH2CH2CHO CH3CH2CH2CH2OH
Ether
LiAlH4
CH3-CO-CH3 CH3-CHOH-CH3
Ether
2. Lithium aluminium hydride is not a stronger enough as reducing agent to reduce a double bond unlike H2
which can reduce both the double bond and the carbonyl group.
LiAlH4
CH3CH2CH2CHO CH3CH2CH2CH2OH
Ether
LiAlH4
CH3-CO-CH3 CH3-CHOH-CH3
Ether
LiAlH4//Ether CH3CH=CHCH2OH
CH3CH=CH-CHO
H2/Ni/heat CH3CH2CH2CH2OH
3. From esters
Esters on hydrolysis in the presence of mineral acid or alkalis produce alcohols and carboxylic acids.
O H3O+or HO-
+ H2O R-COOH + R,-OH
R C
OR,
Ester Acid alcohol
H3O+
CH3COOCH2CH3 + H2O CH3COOH + CH3CH2OH
O 2H2/Ni or LiAlH4
R CH2OH + R'OH
R C ,
OR
Ester
Note: Inspite of LiAlH4 we can also use NaBH4, KBH4 by H- attack specifically on C=O group followed by
hydrolyses.
O OH
1.R''-MgX R'
+ R'-OH
R' 2. H2O
R O R R''
4. From Grignard reagent (Organomagnesium)
71
Mg H2 O
R X R MgX R H + Mg OH
eher
O OMgX
H2 O
R MgX + H C R C H R CH2OH
Primary
methanalH H alcohol
R,
O OMgX
H2O
R MgX + R' C R C H R CHOH
Secondary
aldehydeH R, alcohol
R,
O OMgX
H2 O
R MgX + R' C R C R,, R C-OH
aldehydeR
,,
R, R''
tertiary
alcohol
3. Reaction of Grignard reagents with epoxides

1 )
O
R M g X R O H
2 )H 2 O
p rim a ry a lc o h o l
w ith in c re a m e n t
o f 2 c a r b o n to R
,
R
1 ) ,
R
O
R M g X R
2 )H 2 O O H
S e c o n d a ry a lc o h o l
w ith in c r e a m e n t
o f 2 c a rb o n to R
,,
R ,
R
,,,
R
1 ) ,
R
O
R M g X R
2 )H 2 O O H
T e rtia ry a lc o h o l
w ith in c re a m e n t
o f 2 c a rb o n to R
Notice:
• Grignard reagents react with carbon dioxide gas and then hydrolyzed to form carboxylic acid.
• Grignard reagents react with alcohols to form alkanes
• Grignard reagents react with acid chlorides to form ketones
4. From primary amine to give primary alcohol
Primary amines react with nitrous acid to produce primary alcohols
72
NaNO2/HCl
R NH2 R-OH + N2
heat
OH
NH2
NaNO2/HCl
heat
5. By fermentation of carbohydrates
This method is mainly used to prepare ethanol industrially. Ethanol is prepared from starch (e.g:
maize, cassava, millet, sorghum) and sugar (molasses) by fermentation process.
Fermentation can be defined as a sequence of chemical changes in organic substances produced by the action of
enzymes produced by microorganism generally.
Alcoholic fermentation being the process in which enzymes act on carbohydrates to give simpler compounds like
ethanol(alcohol) and CO2.
(a) From starch: malt obtained either from maize grain , millet, or cassava contains an enzyme called diastase
which catalyses the hydrolysis of starch to maltose
(C6 H10O5 )n + n H 2O → n (C12 H 22O11 )
2 2 maltose
At room temperature, yeast is added and one of its enzymes called maltase catalyses the hydrolysis of
maltose to simple sugar so called glucose.
maltase
C12H22O11 + H 2O 2 C6H12O6
maltose Glucose
Finally another enzyme of yeast called zymase catalyses the decomposition of glucose to ethanol.
Zymase
C6H12O6 2 CH3CH2OH + 2CO2
(b) From sugar

Molasses containing sugars is mixed with water and yeast and then allowed to ferment for several days after
which ethanol are obtained during fermentation process.
One enzyme of the yeast called sucrase catalyses the hydrolyses of sucrose present in the molasses to
glucose and fructose.
Sucrase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose glucose fructose
Thus, another enzyme of yeast called zymase catalyses the decomposition of glucose to ethanol.
Zymase
C6H12O6 2 CH3CH2OH + 2CO2
The ethanol obtained by fermentation process is only about 11%. This is made concentrated by distillation which
converts it to about 95% ethanol. This on further distillation yields a constant boiling mixture whose composition
does not change (an azeotropic mixture), therefore 100% is obtained by either.
(i) Distilling with benzene as a third component or,
(ii) Adding quicklime (CaO), which removes water.
73
Note: Methanol can be prepared industrially by the reaction of Carbone monoxide and hydrogen at
3000C at a pressure of 200 atmospheres.
300 0C under 200 atm
CO + 2 H2 2000C,5 atm CH3OH
A. ETHANOL
Ethyl alcohol, or ethanol, C2 H5OH, is a clear, colorless liquid, with a burning taste and characteristic, agreeable odor.
Ethanol is the alcohol in such beverages as beer, wine, and brandy. Because of its low freezing point, it has been used
as the fluid in thermometers for temperatures below -40° C (-40° F), the freezing point of mercury, and for other
special low-temperature purpose, such as for antifreeze in automobile radiators.
Ethanol is normally concentrated by distillation of dilute solutions. Commercial ethanol contains 95 percent by
volume of ethanol and 5 percent of water. Dehydrating agents remove the remaining water and produce absolute
ethanol. Ethanol melts at -114.1° C (-173.4° F), boils at 78.5° C (173.3° F), and has a specific gravity of 0.789 at 20°
C (68° F).
The fermentation reaction, represented by the simple equation C6H12O6→ 2C2 H5OH + 2CO2is actually very complex
because impure cultures of yeast produce varying amounts of other substances, including fusel oil, glycerin, and
various organic acids.
Ethanol can be oxidized to form first acetaldehyde and then acetic acid. It can be dehydrated to form ether. Other
products made from ethanol include butadiene, used in making synthetic rubber; ethyl choride, used as a local
anesthetic; and many other organic chemicals. Ethanol can also be mixed with gasoline to form the automobile fuel
called gasohol. Ethanol is miscible (mixable) in all proportions with water and with most organic solvents. It is an
excellent solvent for many substances and is used in making such products as perfumes, lacquer, celluloid, and
explosives. Alcoholic solutions of nonvolatile substances are called tinctures; if the solute is volatile, the solution is
called a spirit.
Most industrial ethanol is denatured to prevent its use as a beverage. Denaturing involves mixing ethanol with small
amounts of poisonous or unpleasant substances to make the ethanol undrinkable. The removal of all these substances
would involve a series of treatments more expensive than the federal excise tax on alcoholic beverage.
74
VII.5. USES OF ALCOHOLS
Kind Manufacture Uses

Methyl (wood By destructive distillation of Solvent for fats, oils, resins, nitrocellulose. Manufacture of dyes,
alcohol, wood. Also by synthesis from formaldehyde, antifreeze solutions, special fuels, plastics.
methanol) hydrogen and carbon monoxide
under high pressure.
Ethyl (grain By fermentation of sugar, starch, Solvent for products such as lacquers, paints, varnishes, glues,
alcohol, or waste sulfite liquor. Synthesis pharmaceuticals, explosives; vinegar preparation, perfume
ethanol) from ethylene or acetylene. Direct synthesis;source of energy as well as biofuels or
hydration of ethylene. gasohol;alcoholic drink(as wine beer). Also as 'building block' in
making high-molecular-weight chemicals.
Isopropyl By hydration of propylene from Solvent for oils, gums, alkaloids, resins. Making acetone, soap,
(isopropanol) cracked gases. Also as by-product antiseptic solutions.
of certain fermentation processes.
Normal propyl As a coproduct of air oxidation of Solvent for lacquers, resins, coatings, films, waxes. Also as brake
propane and butane mixtures. fluid, in manufacture of propionic acid, plasticizers.
Butyl (n- By fermentation of starch or Solvent for nitrocellulose, ethyl cellulose, lacquer, urea-
butanol) sugar. Also by synthesis, using formaldehyde, urea-melamine plastics. Diluent of hydraulic
ethyl alcohol or acetylene. fluids, extractant of drugs.
Isobutyl By synthesis from carbon Solvent for castor-oil-base brake fluids. Substitute for n-butyl
monoxide and hydrogen at high alcohol in making urea resins.
pressure, then distillation from
products formed.
Secondary butyl By hydration of 1-butane, formed In making other chemicals such as methyl ethyl ketone. Solvent
in petroleum cracking. in nitrocellulose lacquers. Production of brake fluids, special
greases.
Tertiary butyl By hydration of isobutylene, In perfume making. As wetting agent in detergents. Solvent for
derived from petroleum cracking. drugs and cleaning compounds.
Amyl (pentyl) By fractional distillation of fuel Solvent for many natural and synthetic resins. Diluting brake
oil, a coproduct of ethyl alcohol fluids, printing inks, lacquers. In medicinal products.
manufacture by fermentation.
Ethylene glycol By oxidation of ethylene to Deicing fluid, antifreeze, brake fluid. In production of explosives.
glycol. Also by hydrogenation of Solvent for stains, oils, resins, enamels, inks, dyes.
methyl glycolate made from
formaldehyde and methanol.
Diethylene As coproduct in manufacture of Solvent for dyes, resins. Antileak agent. In gas drying. Softening
glycol ethylene glycol. agent in adhesive printing inks.
Triethylene Coproduct in manufacture of Air disinfectant and dehumidifier. Production of resins,
glycol ethylene glycol. plasticizers.
Glycerol From treatment of fats in In alkyd resins, explosives, cellophane. Tobacco humectant.
(glycerin; soapmaking. Synthetically, from
1-, 2-, 3- propylene. By fermentation.
propanetriol)
Pentaerythritol By condensation of acetaldehyde In synthetic resins. As tetranitrate in explosives. Also as drug for
and formaldehyde. treatment of heart disease.
Sorbitol By reduction of sugar, usually In foods, pharmaceuticals, in chemical manufacture.
corn sugar, with hydrogen. Conditioning agent in paper, textiles, glue, cosmetics. Source of
alcohol in resin manufacture.
75
Cyclohexanol By catalytic hydrogenation of Intermediate in making chemicals used in nylon manufacture.

phenol. By catalytic air oxidation Stabilizer and homogenizer of soaps, synthetic detergents.
of cyclohexane. Solvent.
Phenylethyl By synthesis from benzene and Principally in perfumes.
ethylene oxide.
B. ETHYLENE GLYCOL
The chemical formula of ethylene glycol is HOCH2-CH2OH so known as a diol: ethane-1,2-diol can be
obtained from the intensive oxidation of ethylene, then followed by hydration as follow:
O H2C CH2 H2O
CH2=CH2 CH2 CH2
Unsufficient
O
oxygen from air
OH OH
Dilute KMnO4
Warm
• Ethylene glycol is a viscous liquid due to the presence of two OH group and the boiling point is
1970C while melting point is -300C reason why it can be used as antifreeze and manufacture of
polyesters like Dacron
• It has a sweat taste.
• It is soluble in water but not more volatilized.
It is used in the manufacturing of oxalic acid ( HOOC-COOH) by a simple oxidation
C. GLYCERIN or GLYCEROL
Glycerol or Glycerin is a liquid that is colorless, odorless, sweet-tasting alcohol, C3H8O3, HOCH2-CHOH-CH2OH so
named as propane-1, 2, 3-triol with a specific gravity of 1.26. It boils at 290° C (554° F) and melts at 18° C (64.4° F)
due to the intramolecular forces between 3 hydroxyl group that enhance cohesion therefore increase boiling point and
significantly the viscosity. Liquid glycerol resists freezing but may crystallize at low temperatures. It forms a solution
with water in any proportion, and dissolves in alcohol in all proportions, but is insoluble in ether and many other
organic solvents.
CH2 OH CH2 O NO2

3 HNO3
HC OH HC O NO2 + 3 H2O
Heat
H2C OH H2C O NO2
Trinitroglycerin(TNG)
• TNG knows Nobel’s dynamite is more explosive under heating condition by given off several gases like,
CO2, N2, H2O and O2 followed by the great amount of heat released.
• Simple fats and oils are esters of fatty acids and glycerol. Obtained as a by-product of soap manufacture,
after fats and oils have been treated with alkali to form the soap, crude glycerol is purified by distillation.
76
CH2 O C R CH2 OH
3 N aO H
HC O C O -R HC OH + 3 R -C O O N a
R H ea t so ap
H 2C O C H 2C OH
fats stru c tu re g ly cerin e
O
W h ere R is o f th e g en eral fo rm u la: CH3 (C H 2 ) n : if n = 1 4 :p alm itin e fat

if n = 1 6 : stea rin fat
Other important applications are in the preparation of drugs and toilet articles, including toothpastes; as a plasticizer
in cellophane; and as a moistening agent in tobacco products. Because cheaper products are now available, only 5
percent of the production of industrial glycerol goes into the making of nitroglycerin (TNG) explosives. Because of
its affinity for water and its high viscosity, glycerol is a valuable constituent in stamp pad inks. Pumps for petroleum
products are lubricated by glycerin because it resists dissolving in petroleum liquids. Because of its high viscosity and
its nonpoisonous character, glycerin is a suitable lubricant for food-processing machinery.
VII.6.EXERCICES
I. Complete the following chemical reaction and name the products obtained:
(i) Propan-2-ol + Na
(ii) Propan-2-ol + HBr
(iii) Methylic alcohol + CH3CH2-COCl
(iv) CH3CH2-COOH + methanol
Discus the yields of the reaction in (iii) and (iv)
O 1) NaOH
2) H2O
CH3CH2
(v) O CH(CH3)2
(vi)
L
Cr2O72-/H+
Mg H2O Na CH3CH2I
O
B C D E
CH3I A
Et2 O anhydre
1400CH SO
2 4
G F H
Br2 HOCl
KMnO4,Cold and diluted
M
1. State the condition to pass from C product to L
2. Compare the boiling point of M and C, then M and G.
II. An ethylene alcohol CH3CH=CH-CHOH-CH3, can react or not with the following reagents. In your
motivation if it reacts, give the products.
1. H2/Ni
2. KMnO4diluted under warm condition
3. Concentrated KMnO4 and at high temperature
4. HBr
5. H2O/H2SO4 under warm conditions
77
6. Propyne
7. KOH
8. CH3MgBr
9. Ozone then water
10. ½ O2
III. Predict how can you perform the following organic synthesis from methanol as the unique organic
substance and all possible inorganic compounds:
a) Ethanol b) Propan-1-ol (2 ways)
b) Propan-2-ol c) Butan-2-ol
c) 2-Methyl propan-2-ol d) Ethylene glycol
d) Cyclohexanol
IV. In one or more than one steps and using only mineral compounds, try to suggest the possible ways of transformation
of butan-2-ol in :
a) 2-Bromo butane d) But-1-ene
b) But-2-yne e) CH3CH2COCH3
c) 2,3-dibromo butane f) CH3CH2-CH(CH3)-CN
g) But-1-yne h) 3,4-dimethyl hexan-3-ol
i) CH3CH2-CH(CH3)-NO2 j) butane-2,3-diol
k) CH3CH2-CH(CH3)-NH2 l)CH3CH2CH2COOH
V. Write equations to show each of the following conversions can be effected. In each case indicate the reagent(s)
and the conditions for reaction.
a) Propan-1-ol to propan-2-ol
b) Ethanol to ethoxethane
c) Ethene to ethyl ethanoate
d) Ethanol to ethyne
e) Ethanol to propan-2-ol
f) Ethanol to ethanamide
g) But-2-ene to ethanol
V. A compound X has molecular formula C3H8O
(i) Write the structural formula and names of all isomers of X.
(ii) X reacts with iodine and aqueous sodium to form a yellow precipitate
(a)Identify X
(b)Write the equation for the reaction between X and iodine in the presence of aqueous sodium
hydroxide
(c) State what would be observed if X were reacted with acidified chromium(VI) oxide. Write the
equation of the reaction and name the main organic product.
(iii) When X was heated with excess concentrated sulfuric acid, a gas Y which decolorized bromine
water was evolved.
Write the equation for the reaction between
(a) X and sulfuric acid and suggest a mechanism for the reaction
(b)Y and bromine water and name the product
(iv)Y was used in the manufacture of hydroxybenzene commonly known on the name of phenol
(a)Write equation and indicate the conditions for the reaction
(b) Suggest the reasonable mechanism for the reaction in (a)
VI. (a) A complete combustion of 7.5 g of organic compound M containing Carbon, hydrogen and oxygen
gave 17.8g of CO2 and 9.27g of water. Calculate the empirical formula of M.
(c) When vaporized at 760 mm Hg and 400K, 0.225g of M occupied 100 Cm3.
(i) Calculate the molecular mass of M
(ii) Deduce the molecular formula of M
(iii) Write down the structure formulae and systematic names of all the isomers of M.
(iv) Which one of the isomers you have named in (c)(iii) would you expect to have lowest
boiling point. Motivate your answer.
(d) When one of the isomers of M was warmed with concentrated sulfuric acid a gas Z which
decolorized alkaline permanganate solution was evolved.
(i) Write down three possible structure formulae of Z.
78
(ii) Write an equation and indicate the mechanism for the reaction between HCl and one of the
isomers of Z in (d)(i)
(iii) Let A, B, D and E be treated with the powder of sodium and a gas was given off with pop-
pop motion under the flame of candle. A,B and E turn the acidified solution of dichromate
potassium while D do not but once D is treated by HCl in the presence of ZnCl2,
immediately the cloud appear. On the other hand A does slowly (the cloud appears after 5
minutes) while E and B do not give cloud under room temperature (250C).
(iv) Write down the balanced chemical reaction and observations between A,B,D and E.
(v) Given the fact that other isomers of M were treated with HBr, write the chemical reaction.
VI. Explain the following observations:
a) Phenol has pH of less than 7 while phenylmethanol has a pH of 7
b) Ethanol has the higher boiling than diethyl ether
c) Ethanol gives different products with concentrated sulfuric acid under different conditions.
VII. Try to find out the corresponding chemical product in the following series:
A
Step I
LiAlH4 Na
propyne + water A B C +H2
SOCl2
C HCl
D E 2F +water
Mg CO2/H2O D
A B C E + H2O
anhydous ether
LiAlH4
Na Conc H2SO4
Mixture Propanol + methanol
0
of 3 compounds140-150 C
Which reagent and under which condition the conversion of B to C is performed in step I?
Which kind of reaction is involved?
VIII. (a) Ethanol can be manufactured by the process as known as fermentation of natural substances like
millet and molasses.
(i) Explain what is meant by the term alcoholic fermentation.
(ii) Briefly, describe how ethanol can be manufactured from molasses by fermentation and state
the required condition under which every step is effected taking care on the yield
(iii) What is malt
(iv) Explain how 100% ethanol may be obtained from the product of fermentation
Answer :(a) (i) Fermentation is a process by which micro-organisms(enzymes) act on carbohydrates to give
ethanol and carbon dioxide
79
(ii)In the manufacture of ethanol from molasses, the molasses, water and yeast (are mixed and placed in
container and kept at room temperature (with high yield if we keep around 350C) for several days (from
12hours to 72 according to season change and the area). A froth forms on the surface and carbon dioxide gas is
given off while a dilute solution of ethanol about 11% remains in the container.
(iii)Malt is barley, millet or sorghum, which has been germinated for some times then dried.
(iv)The ethanol obtained by fermentation process is about 11% concentrated. This is made concentrated by a
series of distillations, which convert it to about 95% concentrated. Thus, this 95% concentrated, ethanol on
further distillation does not change in its composition and on its physical appearance. Ideally, 100% ethanol
(absolute) is or can be obtained by addition of quick lime (CaO), which removes the water present leaving
only ethanol.
80
CHAP VIII: ETHERS
VIII.1 Introduction
Ethers are organic compounds which have two hydrocarbon groups joined through an oxygen resulting from the
substitution of H of OH group in alcohol by an alkyl group and responding to general formula R-O-R’.
Hence, they are functional isomeric with alcohols.
From their general structure formula is R-O-R’, we can classify them into 3 classes:
• If R and R’ are both identical (R =R’), we have symmetrical ethers.
CH 3 − O − CH 3
CH 3CH 2 − O − CH 2CH 3
• If R and R’ are different( R≠R’), we have unsymmetrical esters.
CH 3 − O − CH 2 − CH 3
CH 3 − CH 2 − O − CH 2 − CH 2 − CH 3
• The fact that functional group is –O-, we can have cyclic ethers called epoxide of the family of heterocyclic
O
O
compound: (CH2)n
VIII2. Nomenclature and isomerism
In the IUPAC system of naming, ethers are considered as alkoxy derivatives of alkanes reason why the general
naming consist as alkoxyalkane ; in case of unsymmetrical ethers ( i.e where R≠R’) the larger of the two alkyl group
is taken as the parent hydrocarbon.
E.g CH3-O-CH3: methoxy methane
CH3-CH2-CH2-O-CH3: methoxy propane
CH3CH2CH2CH2-O-CH3: methoxy butane
Note: Ethers may also be named by the common system by prefixing the names of the alkyl groups attached to
oxygen before the word “ether”, but in case of symmetric ethers, they are taken as dialkyl ether.
CH 3 − O − CH 3 : Dimethylether
CH 3 − CH 2 − O − CH 3 : Methylethylether
CH 3 − CH 2 − O − CH 2 − CH 3 : Diethylether
CH 3 − CH 2 − CH 2 − O − CH 2 − CH 3 : Ethylpropylether
O
ethyl isopropy ether or
ethoxy isopropane
Note: For unsymmetrical ethers, the simpler (smaller) alkyl group is named first.
Ethers are functional isomeric with saturated monohydric alcohols.
CH 3CH 2OH
E.g. molecular formula C2H6O, The isomers
CH 3 − O − CH 3
Moreover, positional and structure isomers are possible in order to generate symmetric and unsymmetrical ethers
ramified or not.
81
VIII.3. PHYSICAL AND CHEMICAL PROPERTIES
VIII.3.1 Physical properties
1. Ethers are sparingly soluble in water but dissolve in organic solvent since their density is less than 1.00
2. Their melting and boiling point increase with increase in molecular weight because of increasing magnitude of
Van der Waal’s forces with size.
3. The boiling points of ethers are much lower than those of alcohols of similar molecular weight. This is because of
the intermolecular hydrogen bonding which are present in alcohols but are not possible in ethers.
Molecule Molecular weight Boiling points ˚C

CH 3 − O − CH 3 46 -24.9
CH3-CH2-OH 46 78
CH3-CH2-O-CH2-CH3 74 35
CH3-CH2-CH2-CH2OH 74 117.7
4. Ethers are more volatile than alcohols, hence the greatest inflammability attitudes due to lack of stronger cohesion
related to the absence of intermolecular hydrogen bonding.
Briefly, chemically, the ethers are inert, stable compounds, not readily affected by alkalis or acids. Most ethers are
volatile, light, flammable liquids, soluble in alcohols and other organic solvents.
VIII. 3.2 Chemical properties
Due to they are saturated compounds and nun polar, they are relatively chemically inert reason why their chemical
reactions are very few.
(1) Reactions in which the carbon-oxygen bond is broken
(a) Ethers react with hot concentrated sulphuric acid to form alcohols
R − O − R + H 2 SO4  → R − OH + RHSO4
Heat
e.g : CH 3 − O − CH 3 + H 2 SO4 → CH 3OH + CH 3 HSO4

Heat
CH 3 − CH 2 − O − CH 2 − CH 3 + H 2 SO4 heat
→ CH 3 − CH 2 − OH + CH 3CH 2 HSO4
(b) Reaction with halogen acids
Ethers react with cold halogen acids to form alkyl halides and alcohols
R-O-R’ + HI ROH +R’I (cold)

Note: (i) For unsymmetrical ethers, the halogen is attached to the smaller of the two alkyl groups
(ii) Ethers react with hot halogen acids to form only alkyl halides.
R-O-R’ + HI RI +R’I + H2O ( hot )
(c) Ethers can act as the Lewis’s base due to the two non-bonded electron pair on oxygen to form coordinative bonds
with Grignard reagent. This explain clearly why organomagnesium compounds are manipulated in ether solvent but
not in water since in water, there’s a reaction which generate alkanes.
R "
R
R
O M g O
R ' R '
X
82
(d) Splitting of tertio-butyl ether (R-O-C(CH3)3 and tetrahydropyran ether at room temperature in the presence of
HCl as catalyst into tertiobutanol and R-OH.
(e)Combustion of ethers gives carbon dioxide and water:
3(n+m)
+ O2 (n+m) CO2 + (n+m+1) H2O
CnH2n+1-O-Cm H2m+1 2
VIII.4. General methods of preparation.
1. This is done by heating excess primary alcohol with concentrated sulphuric acid or phosphoric acid at about 140˚C
H2SO4 /1400C
2R-CH2OH R-CH2-O-CH2-R + H2O
CH3CH2-OH + CH3OH 
H 2 SO4 ∆
→ CH 3 CH2 -O-CH 3 + H2O
CH2OH CH2
CH2
H2SO4Conc O
1400C
Note: The temperature should be carefully controlled so as to be between 130° and 150° C (266° and 302° F),
because at higher temperatures the ether reacts further, yielding ethylene gas. The crude ether is purified by shaking
with limewater (to remove acidic contaminants) and then with anhydrous calcium chloride (to remove unreacted
alcohol and most of the water), and redistilling. Although containing small amounts of water, this ether is suitable for
most purposes, including surgical use. If subsequent redistillation is made in the presence of phosphorous pentoxide
or metallic sodium, the final product, absolute ether, is free of water and alcohol.
3. From alkyl halides( WILLIAMSON Synthesis)
(a) In this method alkyl halides are heated together with sodium or potassium alkoxides.
Cu / ∆
R O Na + R’-X → R'−O − R + NaX
(b) In the second method, the alkyl halide is heated with dry silver oxide and gives precipitate.
2 R − X + Ag 2O  → R − O − R + 2 AgX
heat
e.g : 2CH 3 − Cl + Ag 2O heat


→ CH 3 − O − CH 3 + 2 AgCl
2CH 3 − CH 2 − Br + Ag 2O → CH 3 − CH 2 − O − CH 2 − CH 3 + 2 AgCl
heat
VIII.5. USES
• Ether itself is one of the most important organic solvents and is widely used in the laboratory as a solvent for
fats, oils, resins, and alkaloids.
• A mixture of ether vapor with air is violently explosive; moreover, on long standing, ether may be partly
oxidized to an explosive peroxide compound( R-O-O-R). Ether must therefore be stored and used with great
care.
• Its principal uses are as a solvent, as a starting material for manufacture of chemical products, and as an
anesthetic.
• Anisole (methyl phenyl ether or methoxy benzene) is used as perfume and flavoring due to its pleasant smell
and high volatility.
• Diethyl ether commonly known as ether is most suitable for surgical uses.
83
VIII.6 EXERCICES
I. Name the following compound according to IUPAC nomenclature:C2H5-O-CH(CH3)2 b) O(n-C4H9)2

CH3 CH3
O H
c) CH2=CH-O-CH2-CH=CH2 d) H
O
CH3
O
CH3
II. Replace each alphabetic letter by the exact chemical compound in the following sequence
H2SO4 CH3ONa HCl
1. A HI C D
propnan-1-ol B
1700C 250C
HBr H 2O CH3CH2I CrO3
2. Propene A Na D E
B C
H2O2
HClO A Water Na ICH3 Water E
3. Ethylene B C D
Oxyde d'ethylene HCN H2SO4 CH3CH2MgCl E
4. A B D
Heat at O
5. 1700C O
1.
Mg anhydous F G + Mineral products
Br
2.H3O+
F
3.water
L + Mineral
products
(i) State functional isomers of G and provide the efficient chemical test to distinguish them
H
+ Cl
6. HO H2SO4
A
OH 1400C
Suggest the mechanism of this reaction with concise comment

III. Explain the following concept
1. The boiling temperature of ethanol is greater than the one of its isomer but this isomer is more volatile is
more volatile than ethanol.
2. During the ether syntheses, you have to work under controlled temperature.
3. During the ether the ether storing solvents in the laboratory, some measures and care should be taken.
4. Water is the most used solvent even in organic chemistry than ethanol but ethanol is the best solvent whether
for organic and inorganic compound while ether are good for organic compound.
5. Discus the reason of some uses of ether
84
IV.1. When ether A is treated with hydriodic acid in excess, only one alkyl iodide B with 69.0% of iodine was
formed. The hydrolyze of B gives D which produce immediately the cloud once passed through the concentrated
solution of hydrochloric acid in the presence of zinc chloride.
Suggest the possible developed formula for A, B and D and their name according to IUPAC nomenclature.
Let the atomic mass for I, H and C be: 127;1 and 12 respectively.
Answer: A: (CH3)3 C-O-C(CH3)3 (di neobutyl ether ); B:(CH3)3C-I(2-iodo2-methyl propane; D:(CH3)3C-O-H.
2. The specific density of an organic compound A within reference to air is 3.50.The quantitative analyses of
provides the following percentage: % of Carbon is 70.60 and 13.70 for hydrogen. A does not react with A but when
A is heated with hydrochloric acid give only one alkyl chloride B.
The hydrolysis of B provides organic compounds D let be D1 and D2 which turns green the acidified solution of
dichromate potassium initially orange but in excess and the wet red litmus paper became reddish while the one of
blue litmus change from blue to red.
(i) Identify all involved compound i.e. A, B, D1 and D2.
(ii) State the all possible isomers of A and D1.
(iii)Write all balanced chemical reactions involved
(iv) How can you test B and A
3.The mass spectroscopy of an organic compound that does not react with sodium and silver nitrate or colorless
bromine water has the molecular weight approximately equal to 72g.mol-1.A can not be split into two but A has
geometric isomers .
i. Identify A and state other possible isomers of A.
ii. Complete then the following chemical reactions and give concise conditions and reagents for some steps if
F
PCl5
1.CH3MgI H2SO4 Dilute KMnO4 CH3CH2COCl

A D E G
2. H2O B Warm
1700C heat with perfume
smell
steps and
conditions
necessary. E'
CH3 CH3
H
Answer: A is H O
V. Here there is the structure of molecule A used as drug, perfume so commonly marketed as <anisole> which is
B
O C
CH2OH
OH
OH
O
CH3
H3C
E
A
CH
colorless liquid with pleasant smell and with a sweat taste. D
3
(i) Give their functional group

(ii) Give at least any three functional isomer of A
(iii) State any other two uses of A
(iv) State among the following structure which are isomers and relationship between D and E.
85
CHAP IX: AMINES
IX.1 Introduction and definition
Amines are organic compounds considered to be derived from ammonia by replacement of the hydrogen atoms of the
ammonia with one or more alkyl or aryl groups.
The functional group is –NH2
Thus the amines can be classified in three classes:
• Primary amine(R-NH2) resulting from one replacement of only one hydrogen of NH3
• Secondary amine resulting from a replacement of two hydrogen of ammonia by alkyl group ( R and R’ ) or
aryl group(Aryl) group let be R-NH-R’
R'
N R
• Tertiary amine if all the hydrogen have been replaced by alkyls or aryl groups let be R" e.g.
H3C H3 C H2CH2CH3C
N CH3 N CH3 N CH2CH3
CH2CH3 , CH3 CH3
Note: ( i) If the alkyl groups are the same, we have symmetric amine and else are unsymmetrical amine
(iii) In nature, amine exist as natural product in plants concentrated in leaves as alkaloids like nicotine,
morphine, cocaine and also in animals like fishes most characterized by a pungent smell when they are
dry.
(iv) A part from three classes of amines above discussed, we have quaternary ammonium salts considered as
derivatives of ammonium salts but with replacement of all four hydrogen by alky groups:
R"'
"R R
_
N X
+
R'
IX.2 Nomenclature and isomerism
According to IUPAC, amine are named as aminoalkanes or alkyl amine for especially primary amine but secondary
amine and tertiary amine particular nomenclature is awarded for symmetrical and unsymmetrical.
• Primary amine: They are named as amino hydrocarbons (alkanes, alkenes or alkynes) or alkylamine or
arylamine.
CH3CH NH2 : isopropylamine or
2-amino propane
CH3 NH2 ; amino methane or CH3
methylamine NH2
CH3CH2CH2 NH2 :amino propane : Phenylamine

aniline
or propylamine
NH2
: Ally amine
3-aminopropene or propenamine
• Secondary and tertiary symmetric amines are named as dialkyl and trialkyl amines or as alky amino
CH3-NH-CH3 : Dimethyl amine
alkanes: methyl aminomethane
86
CH3-NH-CH3 : Dimethyl amine

methyl aminomethane
Diisopropylamine
NH or isopropyl 2-amino propane
CH3
H3C N : Trimethyl amine
or dimethyl aminomethane
CH3
Triphenylamine
N
• Secondary and tertiary unsymmetrical amines are named as alkyl amino alkanes by enumerating from the
smallest alkyl in carbon number or starting the prefix N and –N, N for secondary and tertiary amine
respectively.
e.g.: CH3CH2-NH-CH3:N- Methyl ethylamine or methyl amino ethane
N-methyl(1-methyl)propyl amine
: N,N- ethyl methyl propane HN N-methyl sec-butyl amine
N methy ethylamino propane
H3CH2C-H2C
N CH2CH3 : N,N-diethy propylamine
diethyl aminopropane
CH2CH3
About isomerism, amines exhibit the following isomerism:
• Chain isomerism that arises due to te difference in structure of the carbon chain
• Positional isomerism that arises because of the different positions taken by –NH2 in the same carbon chain
for example 1-amino propane and 2-aminoprpane
• Particular chain isomerism resulting from di or tri substitution concerning only nitrogen position in order to
get primary, secondary and tertiary amines.
Activity 1: Work out to find different isomers whose molecular formula C3H9N and C4H11N and try to name
them according to IUPAC nomenclature.
IX.3 Physical and chemical properties of amines
IX.3.1 Physical properties
1. The first two are are gases, from C3 up to C11 are volatile liquid due to weak intermolecular forces and the
higher ones are solids.
2. The lower members have fishy ammoniacal odor.
3. The lower members are soluble in water but this decreases with the carbon chain that behaves as
hydrophobic parts which do not easily interact with water molecule
4. Because of hydrogen bonding, they have higher boiling points than alkanes of closed molecular mass. Let us
discuss the data assigned in the following table:
87
Compounds Molecular mass(in g.mol-1) Boiling points( in 0C)

CH3-NH2 31 -7.0
CH3-CH3 30 -89.0
CH3-CH2CH2-NH2 59 49.0
CH3-NH-CH2CH3 59 35.0
(CH3)3N 59 3.5
CH3-(CH2)2-CH2-OH 74 118.0
CH3CH2-NH-CH2CH3 73 55.6
CH3-(CH2)3-CH3 72 36.0
(i) Because nitrogen is less electronegative than oxygen atom, the hydrogen bonding formed by
amines are weaker than those in alcohols of corresponding molecular mass.
(ii) Also because primary amines have more hydrogen atom on nitrogen atom, they form many
hydrogen bonds hence owing to higher boiling points than those of secondary amine of the same
closed molecular weight.
(iii) Because tertiary amine has no hydrogen atom on the nitrogen atom, it exhibits no hydrogen
bonding so it has lower boiling points than secondary or primary amine of corresponding molecular
mass and not quite similar to those of hydrocarbon of similar mass.
• Briefly, the greater the number of hydrogen an amine has, the many hydrogen bonds it can
form hence the higher is its boiling point.
• The less number of hydrogen bonding an amine can form, the most trend to volatile is
reason why most amines are more volatile than corresponding alcohols, therefore become
more poisonous and toxic than alcohol.
IX. 3.2 Chemical properties
1. Basic properties because they are base according to Brönsted definition

Amines dissolve in water to give weakly alkaline solution like ammonia. The solution turns red litmus paper blue.
_
R-NH2 + H2O R-N+H3 + HO
ACID base
Base Conjugated
acid-base acid
couple
By the law of mass action of Peter Wage, we can write the expression of Kb and late the one of pKb defined as
cologarithm of Kb which express the basic strength because the greater the value of of Kb (i.e the smallest pKb), the
more basic is the solution and the molecule fix more easily the released proton.
+
  −
 R − NH 3   HO 

Kb =  and pK b = − log K b
[ R − NH 2 ]
The basic character of amines is due to the presence of non-bonded electron pair on nitrogen atom which donate
electrons.
Therefore, the strength of the base will depend on the availability of the non-bonded electron pair.
For example, methylamine CH3-NH2 is therefore a stronger base than ammonia because of the presence of the methyl
group has a positive inductive (electron pushing).
The methyl group pushes electrons towards the nitrogen atom. This increases the electron density on the nitrogen; the
non-bonded electrons are therefore easily available for proton attraction. Thus, the expected basicity of amines should
be in the order.
Tertiary amine >Secondary amine >Primary amine >CH3-NH2 >NH3 (ammonia).

But the order is Secondary amine >primary amine>tertiary amine>ammonia
The anomalous behavior of tertiary amines is due to steric hindrance i.e. the alkyl groups tend to prevent the
approaching proton while a secondary amine has more basic than primary.
88
• Aminobenzene or phenylamine or aniline C6H5-NH2 is weaker base than aliphatic primary amines because
the non-bonded pairs of electrons on the nitrogen atom become involved with the delocalization in the
benzene ring and hence is less available for proton attraction.
• Briefly, the order of basicity is predicted to be in order:
NH2
CH3
H H CH3
H CH3
N
N
N NH3
CH3
CH3
CH3
Because of these properties, amines react with mineral acids to produce salts which is the most soluble form of an
amine in water than the corresponding amine what can effected during amine extraction from plants for example
during nicotine extraction from tobacco leaves after being dried on sunlight for few days.
AgOH
R-NH2 + H-X R-NH3+X_ R-NH2 + AgX
pH 8
alkyl Heat at 1000C Precipitate
ammonium
halide: salt
Note: These salts formed with mineral acids are regarded as strong electrolytes and therefore their solutions conduct
electricity and their solutions in water are acidic.
Activity2: Take 5 grams of caffeine, and then dissolve in 50 g of boiled distilled water.
Record the observation
Introduce a conduct meter and compare the new value obtained and the one in water. Discuss both results
and conclude.
2. Reaction with nitrous acid
Primary amines react with nitrous acid (obtained from sodium nitrous and hydrochloric acid) under warmed condition
to give colorless solution (an alcohol) with evolution of nitrogen gas (N2) as the simple observation.
NaNO2 + HCl H
R-O-H+ N2
R-NH2 R N N O
warm
azoic dyes
unstable form
H H NaNO2+ HCl
N CH3CH2CH2-OH + N2 + H2O +NaCl
0
temperature >10 C
CH2CH2CH3
Notice: For aniline reacts and more generally primary react with nitrous acid at temperature above 100C to give
phenol and alcohols but below 100C, aromatic diazonium salts are formed.
(b) Secondary amines react with nitrous acid to give products which are yellow oils called nitroso amines.
R' OH
NaNO2+HCl R' R'
R NH N N O H
warm<100C N N=O
heat
R R nitroso amine
Note: Addition of phenol and concentrated H2SO4 acid to nitroso amine produces an intense blue color
when made alkaline. This is used as a test for secondary amines.
89
(c) Tertiary amines dissolve in nitrous acid to form ammonium nitrite products which on warming
decompose to form nitroso amines and alcohols.
R' OH
NaNO2+HCl R' R'
R N
0 N+ N O- N N=O + R''-OH
warm<10 C "R
R"
heat
R R Alcohol
nitroso amine
Trialkyl
ammonium
nitrite
Note: The reaction of amines with nitrous acid is used to test for the types of amines are used to distinguish
between primary and, secondary, tertiary and aromatic amine.
• But when aniline(aromatic amine) is treated with 2-naphtol and then the hydrochloric acid and
sodium nitrite are added, a bright red solid results. The bright red solid is due to the reaction of
diazonium salt formed by the reaction between the phenylamine and hydrochloric acid and sodium
nitrite with 2-naphtol.This reaction is used to test aromatic amine(See organic chemistry of S6)
N N+ClH32- 2-Naphtol OH
NH2
NaNO2+HCl N N
<100C OH
Phenyldiazonium
bright red solid
Note: Only symmetric tertiary amines are oxidized by H2O2 to give R3N=O: N-oxide trialylamine and water
1. Nucleophilic amines behavior is related to un-bonded electron pair of nitrogen by contributing it in bonding.
4.1 Reaction with acid chlorides and acid anhydride
Primary amines and secondary amines reacts with acid chlorides and acid anhydrides to form amides.
O O
+ HCl
R C
R' NH2 +R C NHR'
acide Cl heat
amine amide
chlorides
O
O
O
C C + R-COOH
Heat R
R' NH2 +R C R NHR'
O
Amide
O
O
C + R"-OH
Heat R
R' NH2 +R C NHR' alcohol
OR''
Ester Amide
O
O
R C + H 2O
+R Heat
R' NH2 C NHR'
OH
acid Amide
This reaction is known as acylation
90
4.2 Reaction alkyl halides

Amines (alky and aryl) halides react with alkyl halides.
R'
R'' R
R'' X
_ R NH N tertiary
R NH2 + R' X
pH 8
pH 8 amine
Primary secondary R'
amine amine
R-X
R''''
R'' +
N R
X_
R'
IX.4 Preparation of amines
(i) From alkyl halides(Hoffman method): In this method, alkyl halides are heated with concentrated ammonia
solution to a temperature of about 1000C in a sealed.
Reaction gives rise to all the three types of amines further more quaternary ammonium salts.
R'
R'' R
R'' X
_ R NH N tertiary
R NH2 + R' X
pH 8 pH 8
amine
Primary secondary R'
amine amine
R-X
Heat R''''
1000C R'' +
N R
X_
R-X + NH3 R'
Note:
• This method is not useful because a mixture of products are obtained. The mixture of products can however
be separated by fractional distillation sine their boiling points are quite different.
• The primary amine is obtained if excess ammonia is used while use of excess alkyl halides lead to tertiary
amine under pH 8 (in alkali).
• You should also precipitate the halides using silver hydroxide AgOH in order to make easier separation
since also it acts as an alkali reagent and do not heat at high temperature.
(ii) From alcohol (SENDERENS method)
In this method, alcohol is heated with ammonia at temperature of about 3000C in the presence of a small amount of
the powder of Al2O3 as a catalyst.
R R R
0
Al2O3/ 300 C R-OH R-OH
NH3 + R-OH NH N
R-NH2 Al2O3/300 C 0
Al2O3/3000C
-H2O
R R
(iii)Reduction of nitrogen compounds
• Nitriles, amides (primary, secondary and tertiary), nitro compounds :are reduced using powerful reducing
reagent like LiAlH4, NaBH4, H2/Ni, Na/alcohol, Sn in the presence of concentrated HCl then conduct
at pH 8 .
91
N
C LiAlH4 H2N
R CH2
R'' nitrile
H R
H Amine
N O
LiAlH4 R''
R'
N R
R
Amide R'
amine
O
O R H
N Reducing species
R N
H
R R'' Primary amine
Reducing reagent R H
R''
C N
C N
R'
R' H
(iv) From primary amide

The treatment of amides with bromine in a solution of potassium or sodium hydroxide (generation of potassium or
sodium hypobromite: KOBr or NaOBr) and heating produce primary amine with the evolution of a colorless, odorless
which turn milky the lime water(CO2).
O
+ Br2 + 2KOH R NH2 +2KBr +CO2 +H2O

R C Heat
NH2 Amine
O
+ Br2 + 2KOH CH3CH2CH2 NH2 +2KBr +CO2 +H2O

H3CH2CH2C C
Heat
e.g. NH2 Prppylamine
Note:(i) The amine prepared has one carbon atom less than amide
(ii) This reaction is used to test primary amide
(iii)Amines can also be prepared by refluxing amides with concentrated solution of NaOH or KOH like
assigned in reaction above (iv) known as Hoffman degradation of primary amide into primary amine.
IX.5 Uses
(i) One of the application of the amines in the preparation of dyestuff especially azo compound; azoic
Compound is any synthetic organic compound that contains two organic molecules linked by an azo
group(Ar-N=N-Ar). This group consists of two nitrogen atoms linked by a double bond. The azo group
absorbs light and gives diverse colors to compounds. Many of them are important dyes or are used in
the preparation of dyes used in photography, as litmus and in tissues.
N =N
H 3C
N -
SO3 Na
+
CH3 M e th y lo ra n g e litm u s
(ii) They are used in histaminic synthesis for example diethylamine

(iii) Amines are useful in biochemistry field like nicotine(extracted from the leaves of nicotiana tabacum) which
is a powerful excitant of central nervous system, caffeine and cocaine(extracted from leaves of a shrub
and chew coca) that acts seriously on CNS as local anesthesia used in medicine as drug.
92
CH3 O
O CH3 N
C OCH3
N
H3C N Cccaine
N
CH3 Caffeine O
N C
Nicotine O N
O
IX.6 EXERCICES
I. Write equation indicating the reagent and condition of how the following conversions can be effected.
(i) Ethane to amino ethane
(ii) Nitrobenzene to phenol
(iii)Ethylamine to ethanol
(iv) CH3CH2CH2CONH2 to propylamine
(v) CH3CN to ethylamine
(vi) CH3CH2CH2CH3 to pentylamine
(vii) Ethylamine to methylamine
(viii) N,N –ethyl isobutyl aniline
II. An organic compound Z containing C, H, and N contains 61.02% carbon and 23.71% nitrogen has vapor density
of 29.50.On treatment with sodium nitrite following by hydrochloric acid gave out nitrogen gaz.
(a)Identify the compound and explain the reaction
(b) Write the equation of reaction of Z with hydrochloric acid. Name the product.
Sn, HCl NaNO2+ HCl K2Cr2O7/H+
CH3CH2CH CH3
A B C
pH 8 heat Heat
NO2
SOCl2
CH3COCl LiAlH4 KCN
G F E D
III. How many amines whose formula is C4H11N and classify them into amines, secondary and tertiary, hence provide
their names according to IUPAC.
(a)How can you distinguish through chemical test these amines?
(b) Starting with readily available materials and proceeding via reduction, show how the above compounds can be
prepared.
(i) Compare and discus the prediction trends of their boiling point and hence to another organic compound B of
molecular formula C4H10O which defines two functional isomers let B1 and B2.
© Among the all isomers state and discuss their basicity trends.
(d)Let A be a saturated amine which is a chiral molecule; define A.
(e) A reacts with one mole of iodomethane in ethanol solvent.Write down the chemical reaction and suggest the
mechanism.
(i) Name the product obtained in (e).
(ii) Which behavior of amine involved in the above reaction.
IV. Complete the following reaction and work out the fixed product:
93
AgOH
1. Isopropylamine + CH3Br 1
excess ammonia
2. Tertiobutylchloride 2
CH CH I AgOH
Triethylamine 3 2 B C+D
3.
4. CH3CH2CH2CHO + NH3 + H2 Ni 4
5. butan-2-ol + ethylamine 5
3000c
1.CH3-NH2
5. CH3-CO-CH3 5'
2.H2/Ni
?
6. CH3CH2-X Propylamine
(one step)
7. Diethylamine + heat at pH8
C6H5-COCl
1.NaNO2+HCl
8.2-aminopropane 8
2.H2O/ heat
H2O2
9.Trimethylamine 9
10. Aniline NaNO2 + HCl
10
V. Work out this sequence of chemical reaction and replace each letter by the compound involved:
2 CH3I AgOH
C5H13N C7H18NI D+E + H2O
heat
A B
Conc KMnO4/H+
E Heat CO2 + CH3-CO-CH3 + H2O
LiAlH4 H2O
A+ CH3-COCl F G
Warm
VI.(i) Arrange the following bases in order of increasing basic character, aminomethane, phenylamine,
ammonia,dimethylamine and triethylamine.
(ii) Explain the order of basic character.
94
CHAP X: CARBONYL COMPOUNDS: ALDEHYDES AND KETONES
X.1 Introduction and definitions
Aldehydes and Ketones compounds belong to a class of reactive organic compounds resulting from a simple
O
replacement of methylene (-CH2-) group by carbonyl group( ) so called carbonyl compounds.

From the above definition, two classes of carbonyl compound are known:
O O
and
R H R R'
Aldehyde Ketone, where R and R can be alkyl or aryl groups, but for aldehydes R can be
hydrogen atom(formaldehyde) or different to hydrogen while for ketones, R and R should be different to hydrogen
atom even though they can be the same or different.
X.2. Nomenclature and isomerism
In the IUPAC nomenclature system, the longest continuous chain having the aldehydes group or ketone group is
taken as the parent chain. The terminal “e” of the corresponding hydrocarbon is replaced by “al” or “one” with its
position number in carbon chain if necessary before one statement.
e.g. H2C=O: Methanal or formaldehyde or formol

CH3-CHO: Ethanal or acetaldehyde
O O
‖
CH3 – CH2 – C CH3 – C – CH3
H,
,
Propanal Propanone or
acetone
O
O O
CH3 – CH – C ‖
CH3 – CH2 – CH2 – C ╿ H CH3 – C – CH2 – CH3
H, CH3 ,
butanal 2-methyl Propanal butan-2-one
95
CH3-CH2-C CH2-CH(CH3)2 :5-methyl hexan-3-one

O
: 3-methyl pent-2-enal
O
H
O O
O
CH3-C-CH CH=CH2
H H O
C
CH3 H2 pentane-2,5-dione
3-Methy pent-4-en-2-one propanedial
O
O
O
CH3
H
Benzophenone
Acetophenone Benzaldehyde
methyl pheny ketone
Aldehydes show chain isomerism, among themselves and functional isomerism with ketones , cyclic ether, and
unsaturated alcohols(enol) that may provide geometric isomers( cis and trans or of E-Z convention).
e.g. C3H6O has the deficiency number number which is 1, therefore represent structure with double bond let C=C,
C=O and a ring or cyclic compounds.
O
O H2 C CH2
CH3 – CH2 – C
CH3 – C – CH3 CH3 – O – CH = CH2
H H2 C O
OH
O CH3
HO-CH2-CH=CH2
cyclic
Alcohol ether Prop-2-en-1-ol
Note: Aldehydes shows functional isomerism with Ketone.

e.g: C3H6O
O
O
CH3 – CH2 – C
CH3 – C – CH3
H
Activity 1.Give all possible molecular (isomers in their varieties) whose molecular formula C2H4O2
Exercise: The same as the above activity 1 but for C4H8O2 and C4H8O.
96
X.3. Physical properties and chemical properties
X.3.1 Physical properties
1. Lower members of Aldehydes and ketones (for n<5) are liquids except formaldehyde which is a gas at room
temperature and are miscible with water and their solution are neutral to litmus. But aldehydes and ketones dissolve
almost all organic compound reason why they can be used as organic solvent.
2. Aldehydes and ketones have higher boiling points than hydrocarbons of similar molecular mass because of their
polar nature which results in some intermolecular attraction. But their boiling points are lower than those of alcohol
of similar molecular mass because of –OH group present in alcohols and allow them to form hydrogen bonding.
Acetone also called dimethyl ketone and 2-propanone, boils at 56° C (133° F), and melts at -95° C (-139° F) while
formaldehyde, can be compressed into a liquid that boils at -21° C (-5.8° F).
3. Aldehydes and ketones are more volatile than alcohols due to absence of hydrogen bonding in their structure.
4. Formaldehyde and liquid aldehydes like have a distinguish smell (pungent smell) while liquid ketones has pleasant
odor due to carbonyl group and are sweet like bonbons (for the solid ketones: fructose which is a ketose) for example
acetone has a mild, pleasant odor.
Activity 2: Butane, propanal and propanone, both of the same molecular weight of 58 g.mol-1 have the following
randomly boiling points in (0C):-0.5;56.1and 49.Assign each compound its boiling points. Why?
X.3.2 CHEMICAL PROPERTIES
Both Aldehydes and ketones have a common functional group C=O in which oxygen atom being more
electronegative than carbon attracts more towards itself thus acquiring a partial negative charge while the carbon
carries a partial positive charge. Hence carbon oxygen bond is thus polarized, therefore nucleophilic reagents and
bases will attack the electron deficient carbon with the result that its electrons are shifted towards the oxygen atom.
The anion formed then takes up a proton to give the end product.
O A
O
+ _ B R'
A B- +
R' R R
H
O
+
H+ + O O H
+
Nu_
H
O
Nu
The above reaction represents an addition on Carbon carrying oxygen atom and on oxygen of carbonyl group.
The carbonyl group in Aldehydes will be more reactive than in ketones. This is because in ketone, due to presence on
two alkyl groups which have positive inductive effect, the charge on carbonyl carbon will be highly neutralized with
97
the result that any attacking Nucleophilic is less attracted. Because of this, methanal without any alkyl group, will be
more reactive than any Aldehydes and all ketones.
Note: The greater the size of the alkyl group attached to the carbonyl carbon, the less the reactivity because the large
groups around the carbonyl group hinders the attacking nucleophilic from reaching the positively charged carbon.
This is called steric hindrance.
E.g. the order of reaction of the following is

CH 3CH = O > (CH 3 ) 2 CO > (C 2 H 5 ) 2 CO > (C3 H 7 ) 2 CO
If the hydrogen atoms on the carbon next to the carbonyl group are replaced by electron withdrawing groups, the
reactivity is increased.
CH 3 − CH − CHO is more reactive than CH 3CH 2 − CHO
e.g.: |
Cl
A. Reactions which are undergone by both Aldehydes and ketones
1. Reaction of the alkyl groups

(i) Halogenation : Both aldehydes and ketones react with halogens in which the hydrogen atoms on the carbon next
to the carbonyl group (α-hydrogen) are replaced by the halogen atoms. This reaction is catalyzed by any stronger base
that can remove the hydrogen in α-position of carbonyl group due to negative inductive effect exerted by carbonyl
group to its neighboring chain.
H O
R' X2/NaOH X
O O R'
H X2/NaOH
R'
_HX _HX R
H R R X
X
H O
H3C Cl2/NaOH Cl
O O H3C
H Cl2/NaOH
H3C
_HCl _HCl CH2CH2CH3
H CH2CH2CH3 CH2CH2CH3 Cl
Cl
O
O
Br Br
4 Br2 /excess Br Br
NaOH
+ 4HBr
Notice: This reaction respects the mechanism that goes through enolate ion which generates enolic form, the unstable
form that can be converted in ketone according to keto-enol tautomer equilibrium so called tautomeric equilibrium
that leads to tautomeric(the property permitting some compounds to exist as a mixture of two isomers that are
interconvertible and thus in equilibrium).
(ii) Alkylation consists of addition of alkyl group released by alkyl halides in concentrated NaNH2 in α-position of
carbonyl group of an aldehydes or a ketone due negative inductive effect of carbonyl group against neighboring
group.
98
O
O
NaNH2 + HX
R"-X R
R
CH R'
CH R' heat 1000C
R"
. H
2. Reaction of the carbonyl group
(a) Reaction with hydrogen (Reduction)
Both Aldehydes and ketones are reduced by hydrogen in the presence of catalyst like Ni, Pt,or Pdto primary and
secondary alcohols respectively.
R − C O H + H 2  N → R C H 2 O H (p rim a ry a lc o h o l)
i / heat
R − C O − R ' + H 2  N → R C H O H − R '(s e c o n d a r y a lc o h o l)
i / heat
Note: (i) Reduction also can be effected by use of LiAlH4, NaBH4 or Na /Alcohol.
CH 3CH 2 − CHO + H 2 →
Ni / heat
CH 3CH 2CH 2OH
CH 3CH 2 − CO − CH 3 + H 2 →
Ni / heat
CH 3CH 2CHOH − CH 3
(ii) This reduction can be enhanced only for ketones to alkanes in the presence of concentrated hydrochloric acid zinc
amalgam powder as a catalyst through Clemmensen reduction; or , using hydrazine in the presence of alkali( KOH)
by a special reduction called Wolf Kishner reduction).
O
Zn-Hg/HCl
CH2
R R' Or NH2-NH2/KOH R R'

alkane
Ketone
(b) Addition of hydrogen Cyanamid

Both Aldehydes and ketones react with KCN in the presence of H2SO4(or H-CN) to produce 2-hydroxyl nitriles or
cyanohydrins
Note: HCN can be generated in situ by the reaction between KCN or NaCN with sulfuric acid.
H2SO4 +KCN→KHSO4+HCN
H H O
O 2 H2O
H C N R C N R C
+ OH
R H OH OH
Aldehyde alpha-hydroxy
Cyanohydrine
carboxylic acid
O
OH OH
O
NaCN+ H2SO4 2 H 2O
OH
H3 C C H3C
H3 C H N 2-Hydroxy prpanoic
H H
or lactic acid
99
O
O OH
OH
CN
H-CN OH
2 H2O
(c) Reaction with sodium hydrogen sulphite (Sodium bisulphite)

Both Aldehydes and ketones react with a saturated solution of sodium bisulphite to give sodium bisulphite products
which are white crystalline solids.
OH
O SO3Na
Aldehyde or ketone sodium
+NaHSO3 bisulphite:
R R'
R R'
white crystaline solid
Aldehyde or NaOH
keton
O
+ Na2SO4 + H2O
R R'
Ketone or aldehyde
Notice: (i) This reaction above allow to extract aldehydes and ketone using selective precipitation in order to isolate
them from a complex mixture and make them more purified reason why the rate of reaction increase from methanal,
ethanal, aldehydes , methyl ketone and finally ketones.
(ii) Aldehydes react more than ketones because the two alkyl groups in ketones offer steric hindrance.
(iii)This reaction allows us to protect aldehydes and ketone against other reagents according to the desired
transformation, the same as water and ethylene glycol which leads to gem alcohols and dioxalane respectively.
OH
H2C-O
R'
O
R HOCH2CH2OH H2O
OH
H2C-O R' R
_
HOCH2-CH2OH R R' H2O Gem alcohol
Dioxalane
(d) Reaction with Phosphorous pentachloride
Both Aldehydes and ketones react with PCl5 to give gem dihalides.
E.g .CH 3CH 2CHO + PCl5 → CH 3CH 2CHCl2 + O = PCl3
CH 3COCH 3 + PCl5 → CH 3CCl2CH 3 + O = PCl3
100
(e)Reaction with Grignard reagents (organomagnesium)

OMgX
O
H2O
R MgX + H C R C H R CH2OH
Primary
methanalH H alcohol
OMgX R,
O
H2O
R MgX + R' C R C H R CHOH
Secondary
aldehydeH R, alcohol
OMgX R,
O
H2O
R MgX + R' C R C R,, R C-OH
aldehydeR
,,
R, R''
tertiary
alcohol
3. Condensation reactions
Both Aldehydes and ketones react with compounds containing –NH2 with loss of water molecule. The products of
these condensation reactions are brightly colored (yellow or orange) crystalline solids with sharp melting points
which is used for identifying them.
N Y
O
heat 1000C + H2O
+ NH2 Y
_
H2O R'
R R' R
Note: Y can be one of the following groups
• –OH: (NH2OH: Hydroxylamine) to produce oxime
• –NH2 (NH2-NH2: Hydrazine) to produce Hydrazones
• H: H-NH2(ammonia) to give imines from the intermediate unstable form which is iminol
NH NH2
NH
Phenylhydrazine to give phenylhydrazone

NH NH2
NH
O2N NO2
2,4-Dinitro phenylhydrazine
• O2N NO2 Bradey's reagent to give a
yellow precipitate aldehydes or ketone (2,4-dinitrophenyl hydrazones) with tendency to yellow orange on
the sunlight. Note: This reaction is used to test carbonyl group i.e. aldehydes and ketones, with a positive
101
test if a yellow precipitate is formed.

NH – NH2 NH – N = CH – CH2 – CH3
O NO2 NO2
CH3 – CH2 – C +
+ H2O
H
(A) NO2 NO2
Brady reagent
yellow or orange precipitate.
( dinitrophenylhydrazone)
CH3
NH – NH2 NH – N = C
O NO2 NO2 CH3
CH3 – C +
+ H2O
CH3
(B) NO2 NO2
Brady reagent yellow or orange precipitate
( dinitrophenylhydrazone)
NH – NH2
NO2
CH2 = CH – CH2OH + no reaction
(C)
NO2
Brady reagent
O NH NH2
H
N N
O2N NO2
NO2
Cyclohexanone 2,4-Dinitro phenylhydrazine

Bradey's reagent Cycloxanone
heat at about 1000C 2,4-dinitro phenyl
hydrazone:
yellow precipitate NO2
O
O
H2N NH C NH2
• NH C NH2 Semicarbazine to give semicarbazone
102
Note: These reaction take place not at lower values of pH ( between 4.5-6.5) since protons that accelerate the
rate of dehydration but at lower values of pH ,the molecule Y-NH2 will be protonated by H+ and give Y-NH3+
and can not undergo nucleophilic attack against carbonyl group.
Activity2: Suggest the mechanism for the above reaction (Hint that the nitrogen which reacts in phenyl
hydrazine, semicarbazine and in Brady’s reagent is the one with the great number of hydrogen.
Reaction in which Aldehydes and ketones differ.

1. Oxidation reaction
Aldehydes and not ketones are oxidized to carboxylic acids.
Oxidizing agent: can be acidified Cr2O72-, CrO3, H2O2, acidified KMnO4 and O2 from air.
Oxidizing agent like Fehling’s solution, Benedict’s solution or Tollen’s reagents are used.
Note: This oxidation reaction is used to distinguish ketones from Aldehydes since their reactions lead to clear
observations.
(i) When Aldehydes are heated with Fehling’s solution a reddish brown precipitate of copper (I) oxide is
obtained. Fehling’s solution is a mixture of CuSO4.5H2O and sodium potassium tartrate:
KOOC-CHOH-CHOH-COONa in a stronger alkali.
Hence such observations can be explained using the following redox equations.
(i) reduction: 2 Cu2+ + 2 HO_ + 2e Cu2O + H2O

Blue Reddish brown
precipitate
(ii) Oxidation: R-CHO + 3 HO_ R-COO- +2 H2O + 2e
Redox: 2 Cu2+ + 5 HO_ + R-CHO R-COO- + Cu2O + 3 H2O
Blue Reddish brown
precipitate
CH3 COOH + Cu2O

CH3 CHO + CuO
Ethanal blue Acetic acid reddish
brown
precipitate
(ii) When Aldehydes are heated with Benedict’s solution a reddish brown precipitate is also obtained.
(ii) When Aldehydes are warmed with ammoniacal solution of silver nitrate (Tollen’s reagent) a metallic silver
deposit on the wall of the test tube giving silver mirror . This is the silver mirror test for Aldehydes.
(i) reduction: Ag(NH3)2+ + 1 e Ag + 2 NH3 *2
(ii) Oxidation: R-CHO + 3 HO_ R-COO- +2 H2O + 2e *1
Redox: 2Ag(NH3)+2 + RCHO +3HO- R-COO- + 2 Ag + 2NH3+ 2 H2O
Or
103
RCHO + 2 Ag ( NH 3 ) 2 NO3 + H 2O → RCOO − NH 4+ + NH 3 + 2 Ag ( s )
Therefore CH3CH2CH2CHO and CH3CH2COCH2CH3 can be distinguished by this test.

Note: Oxidation of Aldehydes is so easy that even atmospheric oxygen can bring about. That is the reason why most
samples of Aldehydes are found contaminated with variable amounts of corresponding acids what is the case during
the oxidation of ethanol from fermentation to be oxidized fast to acetic acid (vinegar), therefore the win becomes
sour.
Activity 3: Using chemical reactions if possible, give the reagents and the observation that can be used to distinguish
the all isomers of C3H6O.
2. Iodoform reaction.
Only methyl ketones not Aldehydes excluding ethanal undergo this reaction. This reaction can be used to distinguish
a methyl ketone from any other ketones.
E.g. (i) CH 3 − CO − R and CH 3 − CH 2 − CO − CH 2 R or CH 3 − CO − R and R − CH 2CHO
( ii) CH 3COCH 3 and CH 3CH 2CHO
(iii) CH 3CHO and CH 2O
(iv)Ethanol from other alcohols
In this reaction, the methyl ketone is heated with a mixture of iodine solution and sodium hydroxide solution. A
yellow precipitate of triiodomethane is formed.
O O
‖ ‖
CH3 – C – CH2 – CH3 + 3 I2 + 3 HO- CI3 – C – CH2 – CH3 + 3 I- + 3 H2O
O
‖ O
CI3 – C – CH2 – CH3+ I2 + NaOH CHI3 ↴ + NaI + H2O + CH3 – CH2 – C
Yellow precipitate OH
3. Cannizaro reaction
This is a reaction which is only undergone by Aldehydes without α-hydrogen. Here half of the Aldehydes are
oxidized to carboxylic acid and half reduced to alcohol on treatment with aqueous sodium hydroxide. This s an
example of dismutation reaction in organic chemistry. Compare this reaction to those of Aldehydes with α-hydrogen.
It is only undergone by methanal and Benzaldehyde.
O O
2
+ CH2OH
H H H OH H
NaOH
Formaldehyde methanol
Formic acid+
O O
CH2OH
H OH
NaOH
2
+
Benzoic acid Phenyl methanol
104
4. Only Aldehydes with α-hydrogen and not ketones react with concentrated sodium hydroxide solution under a high
temperature at about 1000C in order to facilitate dehydratation process or operate in concentrated sulfuric acid to
give a brown resinous mass containing aldehydes function. The resin is formed after a series of condensation steps so
called condensation polymerization, moreover homopolycondanstion (see polymers in senior 6 for further details).
E.g.
− −
− H 2O
2CH 3CHO 
OH
→ CH 3CH − CH 2CHO  → CH 3CH = CHCHO 
CH 3CHO / OH
→ CH 3CH = CH − CHCH 2CHO
| |
OH: ALDOL OH
CH3CH = CH − CH = CHCHO + H 2O
nCH 3CHO Conc

 → CH 3 (CH = CH ) n CHO
-
OH
The product is thus represented is
Ethanal resin
Note:
• This reaction between two aldehydes (condensation of two units of aldehydes) at low temperature gives an
aldol (organic compound containing aldehydes group and an alcohol group on neighboring carbon atom)
product, hence the reaction is known as aldolization and a Ketol for ketones cases.
The resin can be a natural (semi solid substance secreted in the sap of some plants and trees used in varnish, paints,
inks, adhesive and also in medicine) or synthetic polymer used in manufacturing of petrochemicals and plastic.
• Ethanal through condensation of two units in alkali at high temperature give buta-1,2-diene which is the
lower material in the manufacturing of synthetic rubber.
5. Ketones do not be oxidized by Fehling’s solution, Tollen’s reagent, Benedict solution and other oxidizing
agent like Cr2O72- but concentrated and under high temperature α-hydrogenated ketones on both side are
split into 4 acids
O
H H O
Strongly acidified KMnO4 H O
R R' O
or H2CrO4 R' O H
High temperature + OH +R
+ OH
H H R OH
H R' OH
H
mixture of four carboxlic which is
complexe for separating by fractional
distillation since their boiling point are closed
X. 4. ALDEHYDES AND KETONES PREPARATIONS
1. From alcohols
Primary and secondary alcohols in liquid phase can be oxidized by use of acidified K2Cr2O7, KMnO4, or CrO3 to
Aldehydes and ketones respectively.
+
CH 3CHOH    → CH 3 − C − CH 3
H , heat / K 2Cr2O7
| ||
CH 3 O
105
a)
O O
K2Cr2O7 (acidified )
CH3 – CH2OH CH3 – C + CH3 – C
H OH
Ethanol (A) (B)
Note: one major disadvantage of this method for preparing Aldehydes is that the Aldehydes produced are further
oxidized to carboxylic acids. Further oxidation of the Aldehydes produced can however be avoided by carrying out
the reaction under heat so that Aldehydes which have lower boiling points than corresponding alcohol are removed
from the reaction mixture as soon as they are formed. Therefore the alcohol must be added to the hot oxidizing agent.
In vapor phase both the primary and secondary alcohols can be dehydrated by passing their vapour over heated
copper at 3000C to give Aldehydes and ketones respectively.
CH 3CHOH Cu
/ 300
 → CH 3 − C − CH 3 + H 2
0
C
| ||
CH 3 O
CH 3CH 2OH Cu
/ 300
 → CH 3 − C − H + H 2
0
C
||
O
Also by passing the vapors of the above alcohols together with air over heated silver catalyst , Aldehydes or ketones
are produced.
1
R − CH 2 − OH + O2  → RCHO + H 2O
Ag / 500 0 C
1
CH 3 − CH 2 − OH + O2  → CH 3CHO + H 2O
Ag / 500 0 C
2
1
CH 3 − CH (CH 3 ) − OH + O2  → CH 3CO − CH 3 + H 2O
Ag / 5000 C
2
2. From carboxylic acid
This is done by heating calcium salts of carboxylic acids
(a) When calcium methanoate is heated alone, methanol is produced.
( HCOO) 2 Ca → CaCO3 + H 2CO
heat
Other Aldehydes are produced by heating calcium salt of carboxylic acid with calcium methanoate.
( HCOO) 2 Ca + ( RCOO) 2 Ca → 2CaCO3 + 2 RCHO
heat
( HCOO) 2 Ca + (CH 3CH 2COO) 2 Ca heat

→ 2CaCO3 + 2CH 3CH 2CHO
(b) When calcium salts of carboxylic acids other than that of methanoic acid are heated alone ketones are produced.
(CH 3CH 2COO ) 2 Ca 
heat
→ CaCO3 + CH 3CH 2 − CO − CH 2CH 3
3. From alkenes:
In this method, alkenes are ozonized and diluted with water in the presence of Zn.
106
R − CH = CH − R + O3 → R − CH − O − CH − R  → R − CHO + RCHO + H 2O2

Zn / H 2O
| |
O O
E.g.
CH 3 − CH = CH − CH 3 + O3 → CH 3 − CH − O − CH − CH 3 Zn
/ H

2O
→ CH 3 − CHO + CH 3 − CHO + H 2O2
| |
O O
In case of a mixture of Ketone and Aldehydes are produced, here can be separated by fractional distillation even
though it is not easy to achieve it except retaking again several times.
Note: Zn dust is used so as to decompose H2O2, which would otherwise oxidize Aldehydes produced.
4. From alkynes
When alkynes are passed through hot dilute sulphuric acid in the presence of mercuric sulfate, carbonyl compounds
are produced.
2+
CH 3 − CH 2 − C ≡ CH + H 2 O H  → CH 3 − CH 2 − CH (OH ) = CH 2
2 SO4 / Hg
←
Tautomerism
→ CH 3 − CH 2 − CO − CH 3
5. From acid chlorides

In this method, acid chlorides are reduced by hydrogen in the presence of catalyst like palladium to Aldehydes.
R − CO − Cl + H 2 →
Pd
R − CHO + HCl
CH 3 − CO − Cl + H 2 →
Pd
CH 3 − CHO + HCl
Also organocadmium can react with acid chlorides to give ketones

O
O
2 2 + CdCl2
R' Cd R' +
R Cl R R'
6.From acid anhydrides
Passing the vapor of acid anhydride on manganese dioxide MnO2 that act as a catalyst of decarboxylation with the
evolution of Carbone dioxide. This process is specific to ketones only.
O O
O MnO2
+ CO2
Heat R R'
R O R'
Ketone
Acid Anhydride
Notice: (i) Only aldehydes can be obtained from ethyl orthoformiate once treated with Grignard reagent.
H OCH2CH3 H2O
R MgX + C OCH2CH3 2 CH3CH2OH + R-CHO
OCH2CH3
107
(iii) Only ketones can be obtained from Grignard reagent and nitriles and heat in order to avoid reaction between
ammonia and ketone.
O
2 H 2O + NH3
R MgX + R C N
R R'
Notice: Formaldehyde discovered in 1867 by the German chemist August Wilhelm von Hofmann. It is the simplest of
the aldehydes. Formaldehyde is prepared industrially by heating dry air and methyl alcohol vapor in the presence of a
catalyst, such as copper or silver. More direct processes, whereby formaldehyde is synthesized from carbon
monoxide and hydrogen, have been developed. In one process, water gas is passed over a catalyst at a temperature
between 200° and 300° C (392° and 572° F) under a pressure of 7757 torr (150 lb/sq in). Pure formaldehyde is very
reactive and polymerizes easily (see plastics; polymer in senior 6).
5. USES OF ALDEHYDES AND KETONES

• Formalin is a trade name for a solution containing 40 percent formaldehyde and 60 percent water or water
and methyl alcohol; it is employed as a disinfectant, insecticide, fungicide, and deodorant. Formaldehyde is
used extensively in the chemical industry in the synthesis of organic compounds.
• Its most important use is in the manufacture of synthetic resins, Bakelite ( a strong thermosetting polymer
whose monomers are phenol and formaldehyde catalyzed by strong mineral acid), fertilizers and
preservation of some organic specimens ( anatomic specimen) . Recent tests have indicated that it is a
carcinogen.
• Acetone, a colorless, flammable liquid, CH3COCH3, Completely soluble in water and organic solvents,
acetone is itself an important solvent and is used both in the laboratory and in industry. Enormous quantities
are used as solvents for cellulose acetate in the production of rayon and as a gelatinizing agent for
explosives. Acetone is also used as an ingredient in lacquer solvent and to dissolve gums and resins. It is the
solvent in rubber cement and in some cleaning fluids. Acetone can be prepared in the laboratory by
oxidation of isopropyl alcohol, by heating calcium acetate, or by fermenting sugar with certain bacteria.
Currently, most acetone is produced by the Hock process, which uses as raw materials benzene and propene(
from isopropanol dehydratation) catalyzed by an acid to give isopropyl benzene known as cumene, then
oxygenation process will allow us to produce acetone and phenol.
X.6 EXERCICES
I.A liquid organic compound B containing 66.7% in carbon 11.1% in hydrogen and the rest Oxygen has a vapor
density of 36.
1. Determine its molecular formula and suggest all possible isomers of B (at least 10).
2. Within preoccupation to determine the exact formula of B, the following experiments have been carried out on B
and the following observations were recorded:
(i) B gives a yellow orange precipitate when Brady’s reagent (2, 4-dinitro phenyl hydrazine) was added drop wise.
(a) Give the possible structure of B.
(b) Write down the chemical reaction in (i).
(ii) The acidified potassium dichromate solution turns orange to green when B is added under reflux heating
conditions.
(a)Suggest all possible isomers structure of B.
(c)Write down the balanced chemical reaction above to motivate such observations
(iii)When B is added to sodium hydroxide solution containing phenolphthalein, the solution become firstly colorless
and then after excess sodium hydroxide solution was added to the above mixture with the red litmus paper which
turn blue and stay permanently blue.
(i)Give the formula of B.
(d)Suppose that B is prepared from an alcohol A.
108
(i) Suggest the required conditions in which the above conversions has been effected and determine A with its class
in alcohol classification
(ii)Write the balanced chemical reaction showing the conversion of A to B and the one of B to A.
(iii)How can you distinguish A from its functional isomers A1.
(iv) Is it possible to prepare A from alkenes by hydration under room temperature and concentrated dilute sulfuric
acid as catalyst?
3. Let B1be a special isomer of B which gives a white precipitate with solution of iodine in excess sodium hydroxide
solution.
(i) Identify B1 and motivate your answer using chemical reactions.
II. 1.Give all aldehydes and ketones of the formula C5H10O.

(a)Using chemical reaction to motivate your answer if possible, state the specific reagent and required condition
plus observations to identify through chemical tests these compounds in(1).
(2)Name the reagents and state conditions and observations plus chemical reaction if exist to distinguish the
following pair of compounds:
(i) Acetophenone and phenyl ethyl ketone
(ii)Ethanal and methanal
(iii)Acetone and propanal
(iv)Ethanal and propanal
(v)Propan-2-ol and acetone
(vi) 2, 2-dichloro pentane and 3, 3-dichloro pentane.
III. Write equations to show how each of the following compounds can be synthesized. Indicate the reagent used and
the conditions of reactions.
a. Diethyl ether from ethanal
b. Propanone from propane
c. Propane from propanone
d. Pentane from pentanal
e. Lactic acid from acetic acid.
f. Acetophenone from Benzaldehyde
g. Ethyl benzene from Benzaldehyde
h. Butanone from Grignard reagent.
i. Formaldehyde from inorganic compound via industrial process.
IV. Alcohol class speciation
Two isomers A and B, soluble in water and has no color change on litmus paper burn with no sooty flame and has the
molecular formula C4H10O.
In order to identify them, the following experiments have been carried out on them:
• A and B react with sodium powder, then the evolved gas produce pop-pop motion with the flame of a
candle,
• A was heated in the presence of Al2O3 powder at around 3000C and gives only C that reacts with bromine
water, but A give two products C and D which both give a positive test with bromine water,
• When A is oxidized by acidified potassium dichromate solution gives E that give a positive test with
Tollen’s reagent,
• Once B is oxidized in the same condition to A, gives F which does not react either with Fehling’s solution
and Tollen’s reagent but only a yellow orange precipitate was formed with Brady’s reagent commonly
abbreviated DNPH.
a. From the above results, give the formula and name of A and B. Can they rotate the polarized light once
analyzed through polarimeter?
b. Write the equations corresponding to all above observations.
c. C and D are ozonized in alkali condition. Give the name of the products.
d. Conclude for other alcoholic isomers of A and B. In one step, how can you distinguish them one from
another.
109
V. Complete the following reaction:

H
G
1.CH3MgBr
2. H2O Br2/NaOH
1.O3 1.NaOH LiAlH4

B 2. Heat A D
2.Zn, H2O
H2/Ni
NaHSO4
E
F
VI. Eight (8) organic compounds was found in the chemistry laboratory without labels but they were suspected
among the following chemical structure according to the information provided by lab technician
O
C
H CH3C
H CH3CH2CHOHCH2CH3 HC C CH2CH2OH
O
O
CHOHCH 2 C
O C
CH3CCH3 et CH3-CO-CH2-CHOH-CH2-COH
In fact, their labels were unfortunately detached and randomly mixed. In order to identify the content of each
bottle, they were numbered from 1 to 8 and carry out the a series of experiment that is chemical test and note
the observation by positive ( +) if the reaction occurs and negative (-) in case there is no chemical reaction .
The following table summarizes all observation done for a specific testing reagent.
Number H2/Ni Raney DNPH :2,4- Fehling I2/HO- SOCl2

of the under pression of dinitrophenylhydrazine solution
bottle 1atm
1 + + + - -
2 + + + + +
3 - - - - +
4 + - - - +
5 + + - + -
6 + + - - -
7 + + + - +
8 + + + + -
a. Can you assign each bottle its labels that is to recognize the corresponding chemical content before taking
away labels of each bottle?
b. Name them according to IUPAC.
c. In one or more steps state the scheme through which the following conversion from only mineral
compounds can be effected in order to obtain the product in bottle number five( n05). Note that it is imperious
to give required conditions plus observation recorded along the scheme.
d. State what will happen if we replace Fehling solution by Tolles reagent.
110
e. Write the balanced chemical reaction to motivate the observation done with bottle n08 with Fehling’s
solution.
f. In case the performed test is positive, try to write the balanced chemical reactions.
VIII. An organic compound with molecular formula C2H4O2 has two functional groups that have been
identified as follow :
(i) The first functional group has been identified as follow:
a) The dry compounds A, reacts with sodium to give off hydrogen gases and the formation of an organic
compound B of the formula C2H3O2Na
b) When A reacts with ethanoic acid and 5 ml of concentrated sulfuric acid to give the formation of a
compound R with molecular formula is C4H6O3 and the fruity odor was detected after 10 minutes.
Give the name and the formula of the first group.
(ii) The second group was detected as follow:
(a) 5ml of A was added drop wise to Brady’s reagent and the yellow orange precipitate is observed.
(b)5 ml of A was treated with Tollens reagent which is a solution of Ag(NH3)2+, and the deposit of silver on
the wall of the test tube were observed.
Give the name of the second functional group(name and structural plus formula).
(iii) Give the exact developed formula and name of A.
(iv) Give the geometric isomers of A and state the most stable.
(v) A was oxidized with acidified dichromate potassium solution and give the compound D that
turn red the blue litmus paper and laboratory analyses show that C2H2O4
(vi) A was reduced and give the compound E whose molecular formula is C2H6O2.
State the condition and specify the reagent that allow the above transformation, hence
the name of E.
(vii) What will happen when E reacts with hydrobromide acid in excess quantity.
(viii) Suggest the product that will be formed when E is treated with ethanoic acid and 5 ml of
concentrated sulfuric acid.
Complete the following : A + HCN B
B + 2H2O C
C + NH3 D
111
CHAP XI: CARBOXYLIC ACIDS
XI.1 Introduction and definition

Carboxylic or organic acids are organic compounds represented by general R-COOH or Ar-COOH where R
and Ar are alky group and Aryl groups respectively and –COOH is a carboxylic group characteristic of all acid.
O
R OH . From the above definition, the acid can have one, two or three carboxylic groups reason why we have
mono, di, tri and rarely poly acids according to the number of carboxyl groups present.
O O
Note: The acid contain OH as functional group which contains both carbonyl to which is attached
hydroxyl group –O-H.
XI.2 Nomenclature and isomerism
According to IUPAC system, the acids are named after the corresponding hydrocarbons by replacing the ending
<<e>> by <<oic>>.
• The carboxylic group takes priority to other functional group during numbering in case substituted.
• For diacides, triacide, the ending becomes <<dioic>>.
HCOOH: methanoic acid or formic acid.
CH3COOH : ethanoic acid or acetic acid
CH3-CH2-COOH : propanoic acid or propionic acid
CH3-(CH2)2 -COOH : Butanoic acid or butylic acid( butter)
CH3-(CH2)10 -COOH :Dodecanoic acid or lauric acid
CH3-(CH2)12 -COOH :Tetradecanoic acid or myristic acid
CH3-(CH2)14 -COOH : hexanedecanoic acid or palmitic acid
CH3-(CH2)16 -COOH : octanedecanoic acid or stearic acid.
HOOC -COOH :Ethanedioic acid or oxalic acid.
• Acids with formula HOO-CnH2n-COOH

HOOC-COOH : Oxalic acid or ethanedioic acid
HOOC-CH2-COOH : propanedioic or malonic acid
HOOC – CH2-CH2-COOH:Butanedioic or Succinic acid( se Kreb’s cycle in bilogy)
HOOC-(CH2)4-COOH: hexanedioic or caproic acid or adipic acid(goats)
HOOC-(CH2)8-COOH: decanedioic or sebacic acid
HOOC-(CH2)4-COOH
• Alkenoic acids: CH2=CH-COOH : prop-2-nenoic acid or acrylic acid
CH3-CH=CH-COOH: but-2-enoic acid or crotonic acid

CH2==C (CH3)-COOH: 2-methyl prop-2-enoic or metacrylic acid
CH3 -(CH2)7- CH=CH-(CH2)7- COOH: Oleic acid
• Hydroxy-acids
CH2OH-CH2-COOH : IUPAC : 3-hydroxy-propanoic acid

or β –lactic acid
CH3-CHOH-COOH : α –lactic acid
CH2OH-CHOH-COOH : 1,2- dihydroxypropanoic acid or glyceric acid
112
HOOC-CHOH-COOH: malic acid

HOOC-CHOH-CHOH-COOH: tartaric acid
O
Acetyl salicylic acid
C O O or aspirin(AAS):
H3C Drug used to treat
fever, pain and other inflammation
OH like headache
CH2COOH
H OH
CH2COOH
Citric acid
Mono carboxylic acids show chain and functional isomerism.

Note: Functional isomerism of acid can be ester, aldehydes and ketones with hydroxyl substitution, alkenes with 2
hydroxyl groups (unsaturated alcohol: diol) that may leads to geometric isomerism, and finally ring that can be cyclic
alcohols or cyclic ether, organic peroxides.
Activity1: From the above notice, suggest all possible structure and their relationship whose molecular
formula is
C2H4O2 and C3H6O2, C4H8O2, C5H10O2.
Notice: Optical isomers are also possible as much as the substitution of hydrogen atom increase for example lactic
acid which exists in two isomers that are mirror images of each other, yet they cannot be superimposed on each
other since that molecule has an asymmetric carbon and do not have any symmetric element like centers, axes and
planes.
Just as the right hand and left hand are different, optical isomers (known as enantiomers) are different from each
other and can have different properties. For example, muscles produce D-lactic acid when they contract, and a high
amount of this compound in muscles causes muscular pain and cramps.
On the other hand, sour milk contains L-lactic acid, giving the milk its sour taste
These molecules optical isomers, because the molecules of one isomer will rotate the direction of a beam of plane-
polarized light (light that is traveling in the same plane, not in all directions) in the opposite direction that the other
isomer will rotate he light.
113
Enantiomers are often identified with a D- or L- prefix because of the direction they rotate polarized light.
Enantiomers that rotate polarized light in a clockwise direction are known as dextrorotatory (right-handed)
molecules, and enantiomers that rotate polarized light in a counterclockwise direction are known as levorotatory
(left-handed) molecules.
A solution containing equal amounts of both enantiomers (50% levorotatory and 50% dextrorotatory is known as a
racemic mixture that will not rotate polarized light, because the rotations of the two enantiomers cancel each other
out.
Activity 4: Give all optical isomers of taritric acid (HOOC-CHOH-CHOH-COOH) and determine whether
are enantiomers that can rotate the polarized light in left or right direction. Give the exact name.
XI 3.Physical and chemical properties
XI.3.1 Physical properties
1. Acids with C1-C4 are colorless liquids with a sharp, irritating odor and sour taste, but acetic acid freezes at
slightly below ordinary room temperature reason why it is called glacial acetic acid; mixture of acetic acid with
water solidify at much lower temperature ; soluble in water, C5-C9 are solids only partially soluble in water.
Solubility decreases as the length of carbon chain increases. But Acetic acid is miscible (mixable) in all
proportions with water and with many organic solvents.
2 . Carboxylic acid shows a high degree of association through hydrogen bonding. Because of this, they have high
melting and boiling points comared to other organic compounds of the same mass or derivatives. For example
formic acid boils at 100.50C acetic acid boils at 118° C (245° F) and melts at 17° C (62° F). Hydrogen bonds
enhance the possibility of bringing two acid molecules together forming a dimmer. Hence the molecular mass of
those acids determined from freezing point depression is usually twice the true value for example the molar mass
of benzoic acid is twice its true value since a dimer is considered as a single molecule.
O H
O O
H O
H y d ro g e n b o n d in g
S tru c tu re o f a d im e r in c a r b o x y lic a c id
3. The high solubility of the lower members is also due to hydrogen bond formed with water molecules.
XI. 3.2 CHEMICAL PROPERTIES
The stronger mutually interaction between 2 functional group of carboxylic group such as carbonyl group and
hydroxyl group reject the hypothesis of considering in reactivity acids as an alcohol and a ketone at the same time
but one induce another.
From the above arguments, the reactions of carboxylic acids are classified into:
Reaction involving –H of hydroxyl group O-H
Reaction involving O-H
114
Reaction involving carbonyl group
Reaction involving carboxyl group as a whole system.
Reaction of the alkyl group involving the hydrogen in alpha position from carboxylic acid.
Reaction involving proton release of O-H group
Solution of carboxylic acid turn blue litmus paper red, therefore they are acid moreover weaker than mineral acid
since in water, they undergo dissociation ad release the proton H+ (Arrhenius’s acid definition) which will be fixed
by water as solvent i.e. it exist as hydronium H3O+:
R-COOH + H2O R-COO - + H3O+

Acid base base acid
By law of mass action, we can define the equilibrium constant Ka so called acidity constant that expresses the
strength of an acid because the bigger the value of Ka, the more acidic is the stronger acid.
[ RCOO − ].[ H 3O + ]
Ka =
[ RCOOH ]
Notice: Due to the fact that the value of Ka are so very small, it is more preferable to define it using the
cologarithm concept of Ka in order to make clear the conceptualization of acid strength;hence, pK a = − log K a
Table of acidity behavior and factors influencing acidity
Molecule Ka value pK a = − log K a
H-COOH 1.77X10-4 3.80
CH3-COOH 1.75X10-5 4.75
CH3CH2-COOH 4.90
CH3CH2CH2-COOH 5.20
ClCH2-COOH 2.9
Cl2CH-COOH 1.25
Cl3C-COOH 0.70
HOOC-COOH 1.2
F3C-COOH 0.23
115
Methanoic acid with bigger Ka is therefore a stronger acid than ethanoic acid. The carboxylate ion formed by
ionization of the acid is more stable than the acid because it has many resonance structures.
O
O_ O
O
R _
H+ R
_
R
O R O_
O
O
I II III
Structure I, II, III is resonance structures of the carboxylate ion: the carbon oxygen bond lengths are equal and C-O
length is between than of C-O and pure C=O.
These different values pKa can be explained by inductive effect which is the tendency of an atom or group of
atoms to either donate or withdraw electrons.
Ethanoic acid is a weaker because its methyl group is electron releasing (have positive inductive effect) so that it
pushes electrons towards the O-H bond hence is not easily broken.
CH3 O H
The greater the number of such groups, the greater the effected and therefore the more wekly acidic will be the
acid.
For example, 2,2-dimethyl propanoic is weaker than 2-methyl propanoic acid which is in turn weaker than
propanoic, the same as assigned in the above table, butanoic acid is the most weak acid while in the same section,
acidity strengthen decreases as the alkyl chain increase, hence a stronger acid in the section is the one with lower
pKa or higher Ka.
If in turn an electron attracting (negative inductive effect) group is present, the opposite effect is got. For example,
chloroethanoic acid is a stronger acid than ethanoic acid. This is because chlorine being electronegative, will
withdraw electron electron towards itself thus reducing the electron density around the O-H bond thus weakening.
Hence O-H is easily broken and concentration of hydrogen ion will be the high in solution. Closely, the more
number of such groups, the greater is the effect and hence the more acidic will be the solution reson why trifluoro
acetic acid is more acid than trichloro acetic , dichloroacetic, chloro acetic and acetic because fluorine is more
electronegative than chlorine and hydrogen will strongly withdraw electron towards itself , hence make it easier
the proton leaving.
Cl CH2 C O H
The direction of negative inductive effect:-I
Note: The further away the electronegative element, the less the effect for example 3-chloro butanoic acid is
therefore a weaker acid than 2-chlorobutanoic acid.
116
Activity4:Consider the data in the following table, discuss them and conclude in general
Molecule Ka values pKa
2-chloro butanoic acid 1.39x10-3 ?
Butanoic acid 1.5x10-5 ?
3-Fluoro propanoic 2.29x10-4 ?
(a)Complete the above table by computing the value of pKa after defining pKa.
(ii)Carboxylic acids react with electronegative metals, metal oxide, sodium carbonate, sodium hydrogen carbonate,
NH4OH and alkalis.
Na2CO3
2R-COONa +CO2 + H2O
Na
O R-COONa + 1/2 H2
ZnO Zn
R-COO + H2O
2
R OH
NaOH R-COONa + H2O
NH4OH R-COONH4 + H2O

NaHCO3 R-COONa + H2O + CO2
Notea)The reaction with Na2CO3 and NaHCO3 are used :
(i)In qualitative analysis as test for the presence of –COOH group. Evolution of a gas that turn milky lime water is
CO2 confirms the presence of carboxylic acid.
(ii)To show that carboxylic acids are more acidic than phenols
(iii)Used to distinguish carboxylic acid from phenol and more tertiary alcohols.
(b)The reaction between alkali and alkali earth metals and Zn allows in qualitative analysis to suspect acid OH group
of carboxylic acid which is confirmed NaHCO3 or Na2CO3.
© The reaction with alkalis and metal oxides are called neutralization and allow use to produce organic salts and to
avoid acid effects.
(d)The same acid react with diazomethane (CH2N2) to give product with perfume smell i.e. ester of the class methyl
esters within given off N2.
117
O O
+ CH2N2 + N2
diazomethane
R OH
heat
R OCH3
carboxylic methyl ester
acid
2. Reaction involving –O-H

(i) With alcohol
Carboxylic acid reacts with alcohols in the presence of concentrated H2SO4 to form esters (Esterification reaction).
O O
H2SO4
+ H-O-R' + H2O
R'
Heat at 1000C
R OH R O
O O
H2SO4
+ H-O-CH2CH3 + H2O
Heat at 1000C CH2CH3
H3C OH H 3C O
Activity 5: Write the equation to represent reaction between glycerin and palmitic acid in order to give palmitin
which is a fat ester of high molecular weight that may accumulate in body of palm trees and animals.
(ii)With phosphorus halides, thionyl chloride and ammonia.

O
+ H3PO3
PCl3 R Cl
Cl
PCl5
O + POCl3 + HCl
O
R
SOCl2
Cl R
+ SO2 + HCl
R OH
O
NH3 O
+ H2O
heat at 1000C
R NH2
O O
P2O5 + H2O
R O R
3. Reaction involving carbonyl group

Carboxylic acids are reduced to primary alcohol on treatment with LiAlH4, NaBH4, or by use of hydrogen in the
presence of Ni, Pt or Pd catalyst.
118
OH
H
LiAlH4 /ether pri

R H
OH ma
O H ry
NaBH4 /Ether
R H
R OH al
Ni OH co
H hol
heat
R H
4. Reaction involving the carboxylic group as a whole.

(i)Preparation of alkanes because when sodium salts of carboxylic acids are heated by soda lime (mixture of sodium
hydroxide and calcium hydroxide), alkanes are produced with a shift of one carbon to acid chain.
O
O NaOH NaOH
H + Na2CO3
R
R heat at high T
ONa Alkane
R OH
NaOH NaOH
CH3CH2COOH CH3CH2COONa CH3-CH3 + Na2CO3
T
Ethane
propanoic acid sodium propanoate
O
OH
1.NaOH excess + Na2CO3
2.Sodalime
heat at high
temperature
benzene
Note: (i)This reaction is practically useful in organic synthesis because it is used to reproduce the length of carbon
chain. The following reaction schemes can therefore be derived.
(ii) Carbone dioxide given off is also observed, when heated at high temperature, β-keto acids in order to give
ketones.
Cr2O72-/H+ excess
H2O/H+
H3C CH2OH CH3 COOH
heat
Ethene heat
NaOH(aq)
NaOH(s)
CH4 CH3 COONa
methane heat
Activity 6: Study carefully the following synthesis scheme and replace all letters by organic compound. Suggest the
relationship between C and F and state the role of the reaction involved for both hands.
CN
H2O/H+ H2O/H+ 1.NaOH(aq) 2. Soda lime
B C 3. heat D
A
Heat Heat soda ash
1500C H2/Ni
F
E
119
Note:1. When calcium salts of carboxylic acids are heated aldehydes and ketones are formed(see preparation of
aldehydes and ketones).
2.Methanoic acid, because it contains the easily oxidized group HO-C-H gives a mirror with Tollen’s reagent a
reddish brown precipitate with Fehling’s solution.
5. Reaction involving the hydrogen in α-position from carboxylic group due to negative inductive effect exerted by
carboxylic group make it easier for stronger bases or more electronegative elements like chlorine and fluorine to
substitute hydrogen.
O
O Cl2 excess H
H Cl
H
R
R H
H light Cl
H OH
OH
Activity 7: Give in details how the conversion of ethanol to trichlororo acetic acid can be handled.
XI.4 Methods of preparation of carboxylic acids

1. From primary alcohols and Aldehydes
Primary alcohols are oxidized first to Aldehydes then further oxidation of Aldehydes produce carboxylic
+ +
acid. R − CH 2OH    → RCHO    → RCOOH
K 2Cr2O7 / H / Heat K 2Cr2O7 / H / Heat
+ +
CH 3 − CH 2OH    → CH 3CHO 
K 2Cr2O7 / H / Heat
  → CH 3COOH
K 2Cr2O7 / H / Heat
Note: The use of excess oxidizing agents like acidified K2Cr2O7 or CrO3, primary alcohols are oxidized to carboxylic
acids.
2. By hydrolysis of acid nitriles and acid amides with acid or alkali
+
R − C ≡ N 
2 H 2 O / H heat
→ R − COOH + NH 3
 → R − C−=NH
− H 2 O / H + / heat
R − C ≡ N + H 2O OH O  → R − COOH + NH 3
2
E.g . The following conversions can be possible
(i) CH4 to CH3COOH
+
CH 4 + Cl2 
U .V
→ CH 3Cl + →
KCNAlcohol
CH 3CN 
H 2 O , H / heat
→ CH 3COOH
(ii) CH3CH=CH2 to CH3CH2CH2COOH
CH 3CH = CH 2 + HBr 
peroxide
→ CH 3CH 2CH 2 − Br
+

KCN / Alcohol
→ CH 3CH 2CH 2CN 
H 2 O / H , heat
→ CH 3CH 2CH 2COOH .
Activity 8: How can you perform the conversion of buta-1,3-diene to caproic acid(hexanedioic acid).
3. From dicarboxylic acid

Mono carboxylic acids can be prepared by heating dicarboxylic acids having the 2 carboxylic groups attached to the
same carbon atom.
HOOC − COOH → HCOOH + CO2
Heat
HOOC − CH 2 − COOH → CH 3COOH + CO2

Heat
120
O O
OH
Heat at 1600C OH
+ CO2
OH
benzoic acid
Phtalic acid O
Note: (i) This reaction is used to reduce length of the carbon chain
(ii) The mono carboxylic acid prepared has one carbon atom less than the dicarboxylic acid.
4. In laboratory : CH3COOH can be prepared :
∆
• From its salt: CH3COONa + H2SO4 
→ CH 3 − COOH + NaHSO 4
• From acetylene
O
+ Oxidation
H2O/H CH3-COOH
CH3 C H
HC CH
Hg2+
• From ethanol: CH3-CH2OH + O2 → CH3-COOH + H2O
5. Carboxylation reaction
Grignard reagents react with carbon dioxide gas and then hydrolyzed to form carboxylic acid
O O
Mg
R X
CO2 H2O/H+
R MgX R C R C
Ether
Organomagnesium Heat
OMgX OH
→ R - C -=OH
6.) Oxidation of alkenes: * R-CH=CH-R’  
O + R ' COOH Oxidation
* R-CH=CH2  
→ R - C =O ↑
-OH + CO2 + H 2 O
Oxidation
Notice: The hydrolysis of amide, esters, acid chloride and acid anhydrides provides an acid.
XI 5.Uses
• Acetic acid, prepared by the action of air on solutions of alcohol in the presence of certain strains of
bacteria, such as Bacterium aceti , then dilute solutions (4 to 8 percent) prepared in this way from wine,
cider, or malt are called vinegar. Concentrated acetic acid is prepared industrially. A solution of 5% is used
as an important product of many alimentations.
• Acetic acid is used in the production of acetate rayon, plastics, photographic film, and paint solvents,
cellophane and pharmaceuticals drugs such as aspirin and in perfume synthesis.
• Lead acetate salt is used in the synthesis of ceruse which is a cosmetic product while aluminium and iron
acetate salts are used as mordant in dry cleaner’s.
• Carboxylic acids of high carbon number (n>10) like palmitic acid and stearic acid are used in fat syntheses
that play a key role in soap preparation.
• Carboxylic acid especially diacid play a key role in metabolism for example in Krebs’s Cycle while caproic
acid is used in the nylon-6,6 synthesis.
Activity9: For the following acids, try to give their names (according to IUPAC), their origin and nature
occurrence, isomerism (if exists), physical properties, preparation and conclude by their uses and impacts.
Notice: The following topics should be worked on and presented by students or learners through their research in
group of three persons.
121
• Formic acid
• Acetic acid
• Oxalic acid
• Fumaric and maleic acid
• Lactic acid
• Glyceric acid
• Acetyl salicylic acid or aspirin
• Butyric acid
• Adipic acid
XI.6 EXERCICES
I. Write equations to show each of the following conversions can be effected.Indicate the reagents and state the
conditions involved.
1. Ethene to ethanoic acid 3. Methane to ethanoic acid
2.Ethyne to lactic acid 4.1-bromo-3-methyl to 2-methyl propane
5.bromopropane to propyl ethanoate 6.CH3COCl to ethanal
7.Ethanal to D- lactic acid. 8. Propene to butanoic acid
II. Name a reagent that can be used to distinguish the following pairs of organic compound. State in each case the
observation made
(a) Phenol and benzoic acid

(b) Ethanol and ethanoic acid
(c) Propanoic acid and acetic acid
(d) 2-hydroxy ethanal and acetic acid
III. Complete the following reaction giving the name of the main organic product and its structure formula
F
J
H
1.NH3
NaOH excess
2.Heat
SOCl2 2.Heat at T
1)HCl CN H2O/H+ + LiAlH4

Q A CH3CH2OH/H B C+D
2)KCN CN
Heat Heat at 1000C
Cl2/ligth P2O5
G E
122
IV. Complete the following reaction and specify the function of the main product obtained
heat at high temperature

D D'
Q B
NaOH
Br2/light OH HBr
CH3CH2OH/H+
(CH3CO)2O/H+ COOH A
L 0
100 c
Na2CO3
NH3 E
1000C PCl3
T NH2
F
G
123
CHAP XII: FUNCTIONAL DERIVATIVES OF CARBOXYLIC ACIDS
XII.1 Introduction and definition
The carboxylic derivatives can be classified and defined in the following table
CLASS GENERAL FORMULA EXAMPLE
1.Ester O O
R' CH3
R O H3C O
Methyl ethanoate
2.Acid chlorides O O
: Ethanoyle chlorides
R Cl H3C Cl
3.AMIDES O O
R NH2 H3C NH2

Ethanamide
(a)Monosubstitutes O O
R NHR' H3C NH-CH3

N-Methyl ethanamide
(b)Disubstituted O O
R' CH3
R N H3C N
-CH3
N,N-Dimethyl Ethanamide
R''
4.Acid anhydrides O O O O
ethanoic anhydride
R O R H3C O CH3
5.Nitriles R C N H3C C N : Ethanonitrile
6.Carboxylic salts O O
: Sodium acetate
Sodium ethanoate
R OM H3C ONa
124
From the above table, it is obvious that esters, acid chlorides, acid anhydrides, amides and carboxylic salts have
similarity that is provide by their physical properties and chemical properties but nitriles can be taken apart from the
set even though are acid derivatives.
A. ACID CHLORIDES
O
They have the general formula R Cl .
In their nomenclature, the suffix-ic acid of the acid is replaced by ‘yl’chlorides.

Examples
O
O
CH3CH2C
Cl
Cl O
Propanoyl chloride
: Ethanoyle chlorides
Benzoyl cloride H3C Cl
Note: Their isomers can be chain isomerism, positional isomerism and functional isomerism with chloro aldehydes
and ketones, alcohols with double bond C=C and chlorine as a substituent, cyclic ethers with chlorine, …
Activity 1: Let A be an organic compound which is an acid chloride with formula C3H5ClO.Suggest all possible
isomers of A.
A.1.PHYSICAL AND CHEMISTRY PROPERTIES
A.1.1 Physical properties
Acid chlorides are colorless, volatile liquids with irritating smell due chlorine presence. Their boiling points
are lower than those of corresponding acids due to absence of hydrogen bonding .They fume in moist air.
They are slightly soluble in water but most soluble in organic solvents and their density is closed to the one
of water.
A.1.2 Chemical properties
They undergo nucleophilic substitution reactions more easily than alkyl halides and the attack is one the
positive carbon by the nucleophile.
(i) Hydrolysis: Acids are hydrolyzed in water to form the parent acid.
O
O
H2O
+HCl
R OH
R Cl
Activity 2: Suggest the reasonable mechanism for the above reaction.
(i) Reaction with alcohols: They react with alcohol to produce esters with high yields than Esterification of an
alcohol and carboxylic acid since Cl in acid chloride is a good leaving group than O-H for the case
carboxylic acid
125
O
O
R'-OH
+HCl
R O-R'
R Cl
(ii) Reaction with ammonia and primary amine further more secondary amines to produce primary, secondary
and tertiary amides respectively.
O
+HCl
NH3
R NH2
O
O
R'-NH2 +HCl
R Cl
R NHR'
O
R'-NHR''
R'
+HCl
R N
R"
O
NH2 NH
O
+ HCl
H3 C Cl +
heat
H3C
N-phenyl acetamide
Activity3: Suggest the generalized mechanism of the reactions in (iii) and hence explain why tertiary amines
can not react with acid chloride. If it is possible what would be the expected product.
(iii) The hydrogenation of acid chloride in the presence of Ni gives aldehydes.
A.2.Preparation methods
This is one by heating carboxylic acids with PCl3, PCl5 and SOCl2.
PCl3 +H3PO3
R O Cl
O
PCl5
+ POCl3 + HCl
R Cl
R OH SOCl2
Cl R + HCl
+ SO2
O
SO2 is the most used since it produces gases that can be easily separated to the mixture but it has a negative impact
because it gives SO2 which a green house gas that can lead to green house effect further more concentration in the
atmosphere can lead to acid rain deposition that may cause serious damage in environment whether for living
organism and materials.
126
A.3 Uses
Acid chlorides have no extremely applications in our everyday life but more important in industrial synthesis in
order to increase the yield like in perfume synthesis and nylon-6, 6 as polymer of high importance.
B. ESTERS
B.1 Definition:
O
R'
Esters are organic compounds which conform to the general formula R O where R and R' are alkyl
groups that can be different or identical.
B.2 Nomenclature and isomerism
They are named by first naming the alkyl followed by the name of acid and changing <acid ic> to the
<ate>.
O
CH3
H3C O
e.g.: Methyl ethanoate
O O CH3
O
CH2CH3 CH
CH2CH3
O CH3
H3CH2C O H3C O
Ethyl propanoate Ethyl ethanoate
Isopropyl benzoate
Isomerism in esters compounds can be with acids, aldehydes, ketones, alkenes with double bond C=C and –O-H,
cyclic alcohols and esters and further more geometric isomers.
Activity 1: Give all possible molecular (isomers in their varieties) whose molecular formula C2H4O2 .The same as but
for C4H8O2.
B.3 Physical and chemical properties
B.3.1 Physical properties
• They are colorless liquids or solids with fruity odors; therefore the fruity odor is used as test for
esters in qualitative analysis.
• Their boiling points are less than acids and alcohols of the closed molar mass
• Esters are soluble in water and they are more volatile than acids and alcohols.
Activity 2: The boiling points of acetic acid is 1180C; for ethanol is 780C but closely the boiling points of the
resulting esters ethyl ethanoate is 1020C.Explain why is it so?
127
1.1 Chemical properties

1. Hydrolysis: Esters are hydrolyzed in the presence of H+to alcohols and carboxylic acid.
O O
+
H
+ H2O + R-OH
R'
R O HO- R OH
Activity 3: Suggest the mechanism of the above reaction by labeling the two oxygen atoms with isotopes of
oxygen let O16 and O18 in esters and O16 in water.
Note: Such mechanism was provided by Urey for the first time.
(i) In alkali, this reaction is commonly known as saponification when it is a triester.
O
CH2 O C R CH2 OH
3 NaO H
R H eat so ap
H 2C O C H 2C OH
fats stru ctu re glyc erin e
O
W h ere R is o f th e g en eral form u la: CH3 (C H 2 ) n : if n =1 4 :p alm itin e fat

if n = 1 6 : ste arin fat
Activity4: Discus physical properties of soaps, preparation from animal oils( butter) or vegetable
oil from palm tree known as palmitin, uses and negative impact of misuse of soaps. This
discussion should be done after laboratory work consist of preparing many soap and color them
in yellow, white, blue.
Hence, what are the advantages of coloring soap?
In our experiment, what are the role of ethanol and the heat source at the end?
Explain the mechanism of acting of soap on dirty.
2. Reduction: Esters are reduced with LiAlH4 to two primary alcohols.

O 2H2/Ni or LiAlH4
R CH2OH + R'OH
R C
OR,
Ester
3. Reaction with ammonia to give esters
O O
NH3
R'-OH
R'
R O R NH2
4. Esters react with Grignard reagent, and then hydrolyzed to give tertiary alcohols.
O OH
1.R''-MgX R'
+ R'-OH
R' 2. H2O
R O R R''
B. 4.Esters preparation
128
1. From alcohols and carboxylic acid (Esterification)

Carboxylic acid reacts with alcohols in the presence of concentrated H2SO4 to form esters (Esterification reaction).
O O
H2SO4
+ H-O-R' + H2O
R'
Heat at 1000C
R OH R O
O O
H2SO4
+ H-O-CH2CH3 + H2O
Heat at 1000C CH2CH3
H3C OH H 3C O
2. From alcohols and acid chlorides and acid anhydrides.
O O O O
O
R'-OH R'-OH +R-COOH
+HCl
R'
R O-R'
R Cl R O R R O
Note: Carboxylic metallic salts also produces esters once treated with alkyl halides.
O O
R'-X + AgX
Ag R'
R O R O
Silver acid salts
B.5 USES
• Many esters have a fruity odor and are prepared synthetically in large quantities for commercial use as
artificial fruit essences and other flavorings and as components of perfumes (essential oils from plants)
• All natural fats and oils (other than mineral oils) and most waxes are mixtures of esters. For example, esters
are the principal constituents of beef fat (tallow), hog fat (lard), fish oils (including cod-liver oil), and
flaxseed oil (linseed oil). Esters of acetyl alcohol are found in the head oil of the sperm whale, and esters of
myristic acid and alcohol in beeswax. Nitroglycerin, an important explosive, is an ester.
• Esters such as amyl acetate (banana oil), ethyl acetate, and cyclohexanol acetate are the principal solvents
for lacquer preparations. Other esters, such as dibutyl phthalate and tricresyl phosphate, are used as
plasticizers in lacquers. Amyl acetate is employed as odor bait in grasshopper poisons, and several of the
formiates are good fumigants. Esters also have an important function in organic synthesis.
• Esters have important medical uses for example ethyl nitrite is a diuretic and an antipyretic. Amyl nitrite is
used in the treatment of asthma and epileptic convulsions as an antispasmodic.
• Nitroglycerin and amyl nitrite both cause blood-vessel dilation thereby lowering blood pressure.
• Ethyl chaulmoograte has been used in the treatment of leprosy. Dimethyl sulfate (often used in organic
synthesis as a methylating agent) and diethyl sulfate are extremely dangerous in vapor form and must be
handled cautiously.
C. AMIDES
129
C.1 Definition
Amides are obtained when the –O-H group of –COOH group is replaced by –NH2 , hence amide has the
O
following formula: R NH2 .
From the above definition amide are classified in 3 classes: primary, monosubstituted and disubstituted (see table
at the beginning of chapter IX).
C.2. Nomenclature and isomerism
They are named by replacing the final ‘e’ of the parent hydrocarbon by<amide>. But for most acid that do
not respond to IUPAC nomenclature you have to replace ic by amid and concel the starting word acid.
O O O
CH3
H3C NH2 H3C NH-CH3 H3C N
-CH3
Ethanamide N-Methyl ethanamide N,N-Dimethyl Ethanamide
O CH3
O
CH
N CH3
NH2
CH3
: Benzamide
N,N-isopropyl methyl benzamide
O
H2N NH2
Amino methanamide
amino formamide or urea
Isomerism may be functional isomers with aldehydes, ketones with amino groups and possibility of
different position in chain or rings if possible.
Note: Amides form tautomers with iminol.
Activity 1: Give all possible structure whose formula is C3H7NO and assign them names according to IUPAC.
C.3 Physical and chemical properties
130
1.1 Physical properties.
All amides are colorless crystals except ethanamide which is a colorless liquid. Because of many
intermolecular hydrogen bonding in amides, amides have much higher boiling and melting points than those
of corresponding acids. For example urea has the boiling points of 132.50C.
They are most soluble in water and in organic solvent and they have lower volatilization efficiency.
C.3.2 Chemical properties
1. Amides are hydrolyzed in the presence of mineral acids or alkalis to carboxylic acid.
O O
H2O + NH3
Heat
R NH2 R OH
O
O
R' H2O R'
R N
HN
heat secondary amine
R OH
R''
R''
Carboxylic acid
Activity 2: Suggest the mechanism of the above reactions and motivate the evolution of ammonia under
heat conditions.
2. Reduction: Amides are reduced by LiAlH4, NaBH4, Ethanol/Na to give amines
O
R
H
H R' LiAlH4 N
O H R N
LiAlH4 R''
Ethanol
Ether R NH2 R H
R''
R NH2 Disubstituted amides Tertiary amine
3. Reaction with bromine: When an amide is heated with bromine and alkali, a primary amine is produced
with evolution of a gas that turn milky the lime water and red the blue litmus paper (CO2).
O
heat +H2O
+ Br2 + 4KOH R NH2 + CO2 2 KBr
Primary amine
R NH2 with (n-1) carbon
Amide number of amid
NH2
Br2/KOH
NH2
+ CO2
131
Note: This reaction is used to identify amide that not substituted or primary amides.
• In spite of Br2 in the presence of KOH or NaOH under heat condition we can use sodium
hypobromite or potassium hypobromite.
Activity3: Explain through mechanism approach why mono and Disubstituted amides can not undergo the
above reaction.
4. Amides especially not substituted are dehydrated by action of heat or by P2O5 to give nitriles.
O
P2O5
R C N + H2O
Heat
R NH2
C. 4. Preparation of amides
1. From carboxylic acids with ammonia or NH4OH under heat conditions give amide
O O
NH3 or NH4OH O heat
R OH R NH2
R ONH4 Amide
acid
ammonium
carboxylate
2.From nitriles by hydration under warm conditions.
R C N + H2O
R NH2
2. From acid chlorides, acid anhydrides or esters when they do react with ammonia in order to give amides
especially primary amides, monosubstituted and disubstituted amides in case of reaction between amines
O O
NH3
R'-OH
R'
R O R NH2
132
O O
NH3 O
O
+
warm H
R O R
R O
acid anhydride R NH2
acid amide
O
+HCl
NH3
R NH2
O
O
R'-NH2 +HCl
R Cl
R NHR'
O
R'-NHR''
R'
+HCl
R N
R"
Note: Some amide can undergo internal cyclisation.
O
O
H
N P2 O 5
H Heat NH
OH
O
O
HOBr
N Br
C.5 Uses
Amides have many application as well as in industry and in medicine with focus in pharmacy.
• In medicine: some amide are used as drug and vitamin like Penicellin and nicotinamide
(vit B5).
O
CH3
O
CH
NH2 C N
CH3
O C
CH CH CH3
N CH2 S
C NH
Vitamin B5 Penicillin
A part from these drugs, others are known like diazepam (valium), which acts as a mind-altering by fitting
specific receptors.
133
• In industry as polymers for example nylon-6,6 which is a polyamides.
amide bond
O O
n HOOC-(CH2)4-COOH + n H2N-(CH2)6-NH2 (CH2)4 C NH (CH2)6 NH

HN
nylon-6,6
+ 2n H2O
n
• Nylon is used in the manufacture of fabrics for such articles as hosiery, night garments,
underwear, blouses, shirts, and raincoats. Nylon fabrics are water-resistant; they dry
quickly when laundered and usually require little to no ironing. Nylon fibers are also
used for parachutes, insect screening, medical sutures, strings for tennis rackets, brush
bristles, rope, and fishing nets and line. Molded nylon is used for insulating material,
combs, dishware, and machinery parts.
• In agriculture, they are used as fertilizers like urea:
Because of its high nitrogen content, commercially prepared urea is used in the manufacture of
agricultural fertilizers. Urea is also employed as a stabilizer in nitrocellulose explosives and is a basic
constituent of synthetically prepared resins for example in polyurethane synthesis.
Activity 4: For urea compounds, try to find its origin in nature i.e. nature occurrence, physical
properties, chemical properties by specifying the effect of heat on urea, preparation and
concise uses and negative impact of urea.
D.ACID ANHYDRIDES
1.Definitions and introductions
Acid anhydrides are organic compounds resulting from carboxylic acids by loss of water. Their general chemical
O O
formula is R O R
2.Nomenclature and isomers
According to IUPAC nomenclature, acid anhydrides are named by starting with the name of an acid
without the word acid, then followed by the word anhydride.
O O
ethanoic anhydride
e.g.: H 3C O CH3
134
O O
O O
O
H O H
Methanoic or formic ahydride Benzoic anhydride

H
H
(CH3CH2CH2 CO)2O
O O Butanoic anhydride
O
maleic anhydride
Isomerism can result from atoms connectivity and group function that is functional isomerism with
esters, ketones, aldehydes acids, alkynes with hydroxyl groups, ….
Activity 1: Give all possible structures whose formula is C4H6O3 and define their relationships motivated by their
names according to IUPAC.
3. Physical and chemical properties
3.1 Physical properties
1. Acid anhydrides are liquids with density close to unity, and has high boiling point compared with generating
acids due to molecular weight but low for acid of the same molecular mss due to absence of hydrogen
bonding in acid anhydrides. For example, Acetic anhydride melts at -73° C (-99.4° F), boils at 139.6° C
(283.3° F), and has a density of 1.082.
2. Acid anhydrides are colorless, most volatile, mobile (free flowing since their viscosity is too low) and have
an irritating odor( somehow pungent).
3. They are slight soluble in water but most soluble in organic solvents since their natural occurrence is from
acid dehydration under even room temperature and sun light.
3.2 Chemical properties
They undergo nucleophilic substitution reactions more easily than alkyl halides and esters; and the attack is
one the positive carbon by the nucleophile.
(i) Hydrolysis: Acids are hydrolyzed in water to form the parent acid.
O O
O
H2O 2
R O R
R OH
Activity 2: Suggest the reasonable mechanism for the above reaction.
(ii) Reaction with alcohols: They react with alcohol to produce esters with high yields than esterification
of an alcohol and carboxylic acid since -O-COR in acid anhydrides is a good leaving group than O-H
for the case carboxylic acid
O
O O
R'-OH
+R-COOH
R
R O R O-R'
Ester acid
135
(iii) Reaction with ammonia and primary amine further more secondary amines to produce primary,
secondary and tertiary amides respectively.
O
+ R-COOH
NH3
O R NH2
O
O
+ R-COOH
R'-NH2
R
R O
R NHR'
O
R'-NHR'' + R-COOH
R'
R N
R"
Note: Carboxylic acid obtained in the above reaction can react with ammonia if it is in excess to produce amides
reason why the main product of the reaction is an amide not a mixture of an acid and an amide.
O O O
P2O5
2
heat
R OH R O R
(iv) Passing the vapor of acid anhydride on manganese dioxide MnO2 that act as a catalyst of decarboxylation with
the evolution of Carbone dioxide. This process is specific to ketones synthesis only.
O O
O MnO2
+ CO2
Heat R R'
R O R'
Ketone
Acid Anhydride
4. Preparations of acid anhydrides
Acid anhydrides are only prepared from carboxylic acids by a simple dehydration sometimes in the presence
dehydrating agent like the most commonly used P2O5, H2SO4.
O O O
P2O5
2
heat
R OH R O R
5. Uses
• It is primarily employed as an intermediate in the manufacture of industrial chemicals, pharmaceuticals,
perfumes, plastics, synthetic fibers, explosives, weed killers, and other chemical products.
• About 75 percent of the acetic anhydride produced annually in the United States is used for the manufacture
of cellulose acetate, and about 1.5 percent is used for the manufacture of aspirin.
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OH O O
H3C C O O
OH
(CH3CO)2O CH3COOH
OH
heat
salicylic acid
aspirin(ASA)
Note: Aspirin, trade name for acetylsalicylic acid, the most widely used drug for treating fever, pain, and
inflammation. Aspirin is a synthetic chemical compound that works by interfering with the body’s production of
hormonelike substances called prostaglandins. Often called a wonder drug, it is now thought to have possible
preventative effects against heart disease, stroke, forms of cancer, and other diseases and conditions.
E .NITRILES
1. Definition
Nitriles are organic compounds derivatives of carboxylic acid whose general formula is R C N .From the
general formula, it easy clear that they do not contain oxygen atom and has no remarkable similarity with acids or
acid derivatives.
2.Nomenclature and isomerism
According to IUPAC, nitriles, so called organic cyanide are named by taking the corresponding
hydrocarbons and replacing the ending “e” by “nitrile”or more generally as an acid derivative by
replacing “ic” of the corresponding acid by “onitrile”.
O
P2O5
heat R C N + H2O
R NH2
R X + KCN R CN + KX
e.g.: Nitrile
CH3CH2-CN: propanotrile or propanenitrile
CH2=CH-CN: Propenonitrile or acrylonitrile
N
C
N
C
benzonitrile
Cyclopentane carbonitrile
137
Note: -CN functional group can be taken as substituent in case it is in a molecule containing other
functional groups that take priority on it, such as carboxylic acid, sulfonic acid, esters, acid anhydrides,
and amide.
O
3
NC
: 4-Cyano butanoic acid
OH 1
e.g.: 4 2
Isomerism can result from different connectivity between atoms, therefore functional, chain and
position isomers are possible.
e.g.: For CH3CH2-CN, we can have the following isomers:
HC C CH2-NH2
:Prop-2-yn-1-amine
NH2 C C CH3 : propynylamine or 1-amino prop-1-yne.
NH2 : cyclopropenylamine
CH2=CH-CH=NH : Propenimine and CH2=C-N=CH2
E.3 Physical and chemical properties
3.1 Physical properties
• Organic nitriles or more simply nitriles are liquids most insoluble in water as the number of carbon increase
but soluble in organic solvents, so acetonitrile is a colorless liquid miscible in water reason why is used as
solvents of many reactions and in chromatography.
• They are more volatile than corresponding acid of the same molar weight or derivative acids since they have
no hydrogen bonding.
• Their boiling points and melting points are low comparing to their corresponding acid.
• Their density is almost close to the one of water.
3.2.Chemical properties
Chemical reactions of nitriles are so very few since they are divided into addition (nucleophilic
addition), reduction of triple bonds and late on they can undergo substitution in alpha position. Hence,
they can be summarized as follow:
138
R-CH2-CH2-NH2
R-CH2-CH2-NH2
LiAlH4 i
/N
2
H
H
O 1)R-MgX H2O/HCl
2) 2H2O R C C N
R-CH2-COOH + NH4Cl
R R'
ketones H
1.H2O/H2SO4 R'-
Br
/E
2. warm, 00C TO
K H
O
H R C C N
R
R'
NH2
H
Note: Nitriles can undergo a polymerization to form a hetero cyclic compound with nitrogen as
heteroatom at high temperature and under anhydrous condition.
R
N R N R
C
C P, T,
R
N N N
N
C
R R
E.4 Preparations of nitriles
All nitriles are purely synthetic organic compounds.

(i) From amid and ammonium carboxylate salts, by dehydration
O
P2O5
NH4+ R C N + 2 H 2O
heat: 7000C
R O
-
O
P2O5
heat R C N + H2O
R NH2
(ii) From alkyl halides, once treated with KCN( cyanidation process)
R X + KCN R CN + KX
Nitrile
E.5 Uses
• Due to their high thermodynamic stability, nitriles are used in manufacturing of thermosetting polymers
like polyacrylonitrile(PAN): a polymer of acrylonitrile CH2=CH-CN which is used in the production of
139
acrylicfibers, plastics that resist on heat, and synthetic rubbers.However, in recent years acrylonitrile has
been implicated as a carcinogen.
• Nitriles can be used as organic solvents and also in chromatography.
EXERCISES
I. Using chemical reactions if possible, give the reagents that can be used to distinguish the followed pairs of organic
compounds and give also the observations.
a) CH3CH2NH2 and CH3CONH2
b) CH3COCH3 and CH3CHO
c) Acetic acid and ethanol
d) CH3CH2COCl and n-propyl chloride
e) Ethanonitrile and H-C≡C-NH2
f) CH3CH2OH and CH3CH2CH2OH
g) CH3CH2Cl and C6H5Cl
h) C6H5COOH(Benzoic acid and C6H5OH(phenol).
II. Write equations to show each of the following conversions can be effected. Indicate the reagents and state the
conditions involved.
(i) Ethene to ethanoic acid
(ii) Methane to methyl ethanoate
(iii) 1-Bromo-3-methyl butane to 2-methyl propane
(iv) Bromo propane to propyl ethanoate
(v) Ethanoyl chloride to ethanal
(vi) Propanoic acid to methyl ethanoate
(vii) Ethene to hexanedioyl chloride
(viii) Propanamide to propanamine
(ix) Inorganic compounds to urea
(x) Palmitic acid to sodium palmitate via esterification
III. Complete the following reactions giving the name of the main organic product and its structural formula.
140
NH2
1. CH3CO-O-COCH3+
2. CH3CH2-CO-O-COCH3 + CH3OH
O
H2O/Heat
LiAlH4
NHCH3 A B
H+
3.
Note:A do not react with sodium hypobromite
LiAlH4 2H2O CH3CH2OH LiAlH4 PCl3

B C D
4. E NC CN A
ether Heat stape 1
CH3COCl
A +E F G
IV. (a) Using a named suitable example, outline giving conditions and reagents, how you would effected the
following changes of functional groups in aliphatic compounds:
(i) –COOH to –CN
(ii) –NH2 to –OH
(iii) -CH2OH to –COOH
(iv) – COBr to –CHO
(v) –CN to –COOH
(vi) – CONH2 to -CN
(c) Describe how and what conditions sulfuric acid reacts with each of the following
(i) Propene
(ii) Phenylamine
(iii) Propanone
(iv) 2-hydroxy propanoic acid
(v) Ethanamide
(vi) Phenyl methanol
(vii) Ethyne
V. (a) Describe how and what conditions sodium hydroxide reacts with :
(i) 1, 2-dichloroethane
(ii) Ethanal
(iii)Benzaldehyde
(iv)Ethyl ethanoate
(v)Butanoyl chloride
(b) Using an example, explain what is meant by each of the following terms:
a) Camizaro reaction
b) Saponification
c) Polymerization
d) Ethanoylation
e) Cracking of alkanes
f) Ozonolysis
g) Electrophilic substitution
141
h) Electrophilic addition
i) Elimination reaction
j) Inductive effect
k) Homolytic bond fission
l) Heterolytic bond fission
m) Nucleophilic substitution
n) Nucleophilic addition
o) Condensation reaction
p) Oxidation
q) Reduction
r) Reforming
s) Esterification
t) Etherification
u) Enantiomers
v) Levorotatory and dextrorotatory forms of an enantiomers
w) Racemic mixture
x) Asymmetric carbon
y) Stick formula
z) Hydration and hydrolysis
VI. Three organic compounds Y, W and Z are given as:
OH
O CH2-COOCH2CH3 CH=CH-CO-CH3
O
NH2 C
CH=CH-CH2CH2OH
H
Y W Z
(a) Describe the group functions of the above compounds.
(b) Describe what chemical reactions you would carry out on Y to show the presence of :
(i) The benzene ring
(ii) The ester group
(iii) The amino group
(c) Describe all the possible tests that you can carry out to confirm the formula of W.
(d) Predict the reaction of Z with:
(i) Sodium hydroxide
(ii) Hydrogen gas and finely divided nickel
(iii) Bromine water
(iv) Ethanoic acid
(v) Dilute alkaline potassium permanganate(VII)
(vi) Concentrated and acidified potassium permanganate(VII)
(vii) Acidified potassium permanganate with moderated heat.
(viii) Sodium
(ix) Limestone
(x) Acidified potassium dichromate
IX. (a) An organic compound W contains 60% carbon, 13.3% and the rest is oxygen; but it has a vapor density
of 30.W on oxidation produces Y, C3H6O, which on further oxidation with iodine and sodium hydroxide
solution produce a salt of an acid of formula C2H4O2.On treatment of Y with hydroxylamine, a compound of
formula C2H7NO is produced.
(i) Identify W, Y, and X.
(ii) Write equation of reaction between Y and iodine solution of sodium hydroxide
142
(iii) Suggest a mechanism of reaction between Y and hydroxylamine in the presence of H+.
(iv) Give the appropriate test to distinguish Y and its functional isomer.
(b) Suggest a possible structural formula of each of the following compounds A to D.
• A has a molecular formula C3H6O2 and gives effervescence with sodium hydrogen carbonate and reacts with
phosphorus pentachloride
• B has an empirical formula of CH2Br, on refluxing with aqueous sodium hydroxide give a compound, which
reacts with sodium to give a gas T that burn on candle with pop-pop explosion and do not change any color
of any litmus paper and potassium dichromate paper. Given the fact that 1 mole of B gives one mole of gas
T.
• C has a molecular formula C4H10O and is readily oxidized to give a compound C4H8O, which can be further
oxidized to give a compound R , C4H8O2.
• D with molecular formula C7H7Cl, on refluxing with sodium hydroxide solution and subsequently mild
oxidation gives a compound C7H6O which readily undergoes further oxidation to give compound C7H6O2.
(c)An organic compound A, C8H8O, gave positive Iodoform test and on vigorous oxidation A gave B, C7H6O2,
which was sparingly soluble in water. B after neutralization gave a buff precipitate with iron(III) chloride
solution. B reacted with phosphorus pentachloride to give C, which reacted with concentrated ammonia to give
precipitate D, C7H7NO. Prolonged treatment of D with phosphorus (V) oxide gave E, which could be reduced to
F, C7H9N.
When A was reduced with sodium amalgam, substance G,C8H10O is obtained and gave a positive Iodoform test.
(i) Write structural formulae for substances from A to F.
(ii) Write an equation of reaction of A with iodine and alkali solution.
(iii) Write equation of reaction of B with phosphorus pentachloride.
(iv) Write equation of C with water
(v) Suggest a mechanism of reaction of C with ammonia
(vi) Suggest the appropriate reducing agent under which the conversion of E to F is effected.
Answer:
D is an aromatic compound with a side chain i.e.
CH2OH O
CH2Cl
K2Cr2O7/H+ H
NaOH
Warm Heat
D
K2Cr2O7/H
Heat
O
+
OH
(c)The giving positive Iodoform test confirms the presence of a methyl, CH3-group next to carbonyl group, and due
to the provided formula, we have phenyl methyl ketone known as Acetophenone.
143
CHOH-CH3
F
B: Benzoic acid like most organic acid is sparingly soluble in
water but on warming dissolves in water.
O
Na-Hg
COONa
OH
CH3 Vigorous oxidation
NaOH
A
H 2O
B
l5
COCl PC O
NH2
NH3
HCl+POCl3+ P2O5
Heat
C D
C N
144
CHAP XIII: LIPIDS
XIII.1 Introduction
Lipids, diverse group of fatty substances found in all living organisms are distinguished from other classes of organic
compounds in that they do not dissolve in water but are soluble in alcohol, ether, or other organic solvents even in
petrol.
Among the most important lipids are the phospholipids, which are major components of the cell membrane
Phospholipids limit the passage of water and water-soluble compounds through the membrane, enabling the cell to
keep its contents separate from the outside environment (see biology course of senior 5 for the part of cytology).
Fats and oils, which are composed of triglycerides, serve as stored energy reserves in plant and animal cells. Each
triglyceride is composed of three fatty acid molecules bonded to one glycerol molecule. When an organism has
excess energy available from food or from photosynthesis, it may use that energy to form stores of triglycerides.
These can later be broken down to yield energy when the organism needs it. Fats and oils contain twice as much
stored energy, per unit of weight, as carbohydrates or proteins.
Other important lipids are the waxes, which form protective coatings on the leaves of plants and the skins of animals,
and the steroids, which include vitamin D and several key hormones.
Therefore, according to their structure, chemical composition and physical properties like solubility and melting
points, lipids are classified in three principal classes:
• Glycerides: are triglycerides-esters of glycerol and fat acids including oils and fats
• Sterols which have a large variety of complex molecule like cholesterol and most hormones such as
progesterone, testosterone, and most sexual hormones of course with traces of proteins dissolved within.
• Complex lipids are formed by phospholipids and lipoproteins
XIII.2.Nomenclature classification and physical properties
FATS AND OILS
Fats and Oils, group of naturally occurring organic compounds called triglycerides esters comprised of three
molecules of fatty acids and one molecule of the alcohol gylcerol.
They are oily, greasy, or waxy substances that, in their pure state, are normally tasteless, colorless, and odorless.
Fats and oils are lighter than water and are insoluble in it; they are slightly soluble in alcohol and are readily
dissolved in ether and other organic solvents.
Fats are soft and greasy at ordinary temperatures, whereas fixed oils as distinct from essential oils and petroleum are
liquid. Some waxes, which are hard solids at ordinary temperatures, are chemically similar to fats.
The important difference between oils and fats are liquids is that:
• Oils are liquids and fats are solids at room temperatures i.e. melting point less than 200C.
• Oils contains a large proportion of unsaturated acids like oleic acid in olein while fats contain a large
proportion of saturated acids such as stearic acid in stearin or palmitic acid in palmitin but also with low
melting points.
• Therefore oils can be converted to fats by hydrogenation reaction.
145
Some examples of fats and oils structure:
O
CH2OH (CH2)14-CH3
H2C O C
HC OH + 3 CH3-(CH2)14-COOH O
HC O C (CH2)14-CH3
+ 3 H2O
palmitic acid
CH2OH
glycerol H2C O C (CH2)14-CH3
O
Palmitin or glyceryl tripalmitate
fat(ester)
O
CH2OH
(CH2)16-CH3
+ 3 CH3-(CH2)16-COOH H2C O C
HC OH O
stearic acid + 3 H2O
HC O C (CH2)16-CH3
CH2OH
glycerol H2C O C (CH2)16-CH3
O
stearin or glyceryl tristerate
fat(ester)
Olein which is a fat of oleic acid and glycerol has the following formula and through hydrogenation it can be
converted to fat as shown in the following reaction:
H2C O-CO-(CH2)7-CH=CH-(CH2)7-CH3 H2C O-CO-(CH2)7-CH2-CH2-(CH2)7-CH3
HC O-CO-(CH2)7-CH=CH-(CH2)7-CH3 3H2/Ni
HC O-CO-(CH2)7-CH2-CH2-(CH2)7-CH3
H2C O-CO-(CH2)7-CH=CH-(CH2)7-CH3 H2C O-CO-(CH2)7-CH2-CH2-(CH2)7-CH3
Olein or glyceryl trioleate(oil) stearin Or glyceryl tristearate(fat)
hydrogenation
oil fat
H2C O-CO-(CH2)14-CH3 Palmitic acid unit
HC O-CO-(CH2)7-CH=CH-(CH2)7-CH3 Oleic acid unit
H2C O-CO-(CH2)7-(CH=CH-CH2)3-CH3 Linolenic acid unit
Glyceryl palmitooleolinoleate
The above process creates saturated fats called trans-fatty acids and is done under pressure in the presence of catalyst
at temperature of about 1800C.
Activity1: Give the structure of the molecule resulting from esterification of 2 moles of palmitic acid and one mole of
stearic acid. Provide its name and state whether is a fat or oil.
146
Note: (i) The amount of unsaturation is determined from the amount of iodine absorbed by 100g of fats or oil so
called iodine value or from saponification value. Saponification value is the number of milligrams of KOH required
to completely neutralize (saponify) 1 gram of fat or oil.
Vegetable fats are usually obtained by pressure extraction from seeds and fruit. Animal fats are often extracted from
animal tissue (butter from milk and lard) by boiling fat containing tissue in water and then allowing it to cool. The
heat melts the fat out of the tissue; it then rises to the surface of the water because of its low specific gravity and can
be skimmed off.
Vegetable oil are esters formed from glycerol and long chain carboxylic acids which are obtained from plants like
cotton seeds, sunflower, simsim, castor and groundnuts.
In the extraction of vegetable oil after unshelling or removing the husks, the seeds are then crushed in powder form
and then boiled with water for some time. The oil floats on top of the water. The solid residue is called cake which is
used as animal feeds.
Animal oils are esters obtained from animals such as whale, fish (sardines) and lard oil.
(ii)Fats can be also formed by monohydric alcohols through esterification with fat acids with number of carbons
greater than 16 up to 36.
Complex lipids: Phospholipids and lipoproteins
Living cells contain both simple fats, described above, and other fatlike materials. The latter, which are more
complex substances, include lipids and sterols.
• The so-called phospholipids are derivatives of fatty acids, glycerol, phosphoric acid, and nitrogen-containing
bases.
Fat acid
H2C O COR
HC O COR O quaternary 2-(Amino

CH3 trimethyl) ethanol salt
+
H2C O P O CH2 CH2 N CH3
OH Amine group
CH3
glycerol
group
phoshate group
Lecithin(brain loction)
H2C O COR
HC O COR O
HC O P O CH2 CH NH2
OH Y
Y = H or COOH
Cephalin (brain and spinal cord)
• The glycolipids do not contain phosphorus but are derived from carbohydrates, fatty acids, and nitrogen
compounds.
• Sterols are composed of complicated molecules, each containing 20 or more carbon atoms in an interlocking
or fused ring structure of cholesterol.
• Lipoproteins represent the form under which exist lipids that are present in the plasma fluid or blood. They
are also available as nerves and brain envelops(miningits) in order to protect them. Lipoproteins result from
soluble proteins and lipids like phosphatids in order to facilitate their migration through plasma system.
147
XIII.3 Physical and chemical properties
XIII.3.1 Physical properties
1. Lipids, diverse group of fatty substances found in all living organisms. Lipids are distinguished from other classes
of organic compounds in that they do not dissolve in water but are soluble in alcohol, ether, or other organic solvents
even in petrol.
2. Some are solid for fats and others are liquids for oils but both has specific gravity less than one.
XIII. 3.2. Chemical properties
• Lipids more especially fats which are glycerol-esters undergo unlikely most reaction encountered for esters
due to the condition in which they are stored or their natural occurrence. But the most important concern
hydrogenation only for oil to be transformed to fat under pressure and catalyst as above discussed.
Note: Certain unsaturated oils, such as cottonseed and peanut oils, are often partly hydrogenated to increase their
melting points and make them suitable for use as shortening and cooking fats. Tallow, the animal fats and oils from
sheep and cattle, is used for candlemaking and in margarine. Natural oils that contain esters of unsaturated acids are
known as drying oils and possess the property of forming a permanent dry film when exposed to air. Linseed oil and
other oils of this type are extensively used in the production of paints.
• Fats also serve as a raw material in the manufacture of soap and glycerin through the commonly reaction of
saponification.
O
CH2 O C R CH2 OH
3 N aO H
R H ea t so ap
H 2C O C H 2C OH
fats stru c tu re g ly cerin e
O
W h ere R is o f th e g en eral fo rm u la: CH3 (C H 2 ) n : if n = 1 4 :p alm itin fat

if n = 1 6 : stea rin fat
Note: (i)Soap is a sodium or potassium salt of long chain carboxylic acids obtained by boiling fat or oil with sodium
hydroxide or potassium hydroxide solution.
(ii) Manufacture: Oil or fat is put on a pan and a solution of caustic soda is added. The pan is then steam heated.
Common salt or table salt (NaCl) is then added and the mixture allowed to coll. Soap forms at the surface of the
solution as hard cake which is then removed and processed. Hence, the manufacture of soap is thus a chemical
reaction between esters (oil or fat) and sodium hydroxide(hydrolysis in alkali).
(iii)Sodium soaps are called hard soaps, sodium soaps contain free alkali and are mainly used for washing while
potassium soaps are known as soft soap soap manufactured from good oils and are mainly used as toilet soap and in
marking shaving creams.
148
The cleaning action of soap
Soap mechanism on dirt in cleaning action

This diagram represents the action of soap on dirt in a fabric. Once soap has dissolved in water, its molecules will
surround any patch of dirt on the fabric, forming a ring around it called a micelle. This occurs because soap
molecules have “ends” that differ in their properties. One end is attracted to water (hydrophilic or water loving part
which is polar –COO- ), the other end is attracted to non-soluble substances such as oil and grease (hydrophobic).
When soap molecules attach themselves to grease stains, they form a new surface that is soluble in water. Cleaning
action is the absorption of dirt and grease into the center of soap micelles, which transforms a stain into a soluble
substance that can be rinsed away.
As water molecules attract the polar end the surface tension of water is lowered and repulsion between polar end of
soap and rinsing help remove the dirt.
Note: Soap form scum with hard water. Hard water contains dissolved Ca2+ or Mg2+ which reacts with soap forming
insoluble calcium salt called scum. Formation of scum is expensive in that much soap has to be used to produce
enough lather for washing and it also stains clothes.
Activity2: Through chemical reaction from a washing soap, show how scum is formed when the water used in
washing is from sea or like.
XIII.4 Uses of lipids
• The fats seem to provide a concentrated, efficient source of energy for the cells because the oxidation of a
gram of typical fat releases 9300 calories of energy but, in contrast, the oxidation of a gram of protein or
carbohydrate yields only 4100 calories. Fats also tend to stiffen the cells because they form a semisolid
mixture with water and protect cell and most tissues because they are stored in membrane.
149
• They are very important in animal feeding since they provide enough energy but also great quantity
consumed and non metabolized can lead to overweight and cardiovascular disease like atherosclerosis which
is known for its negative physiological effects.
• They are also especially fats raw material in many industry that produce cosmetic products like soaps and
glycerin; and their waste material can be used in candle manufacturing but of course in detergents and paints
synthesis.
REVIEW QUESTIONS ON LIPIDS
I. (a) What are vegetable and animal oils?

(b)What are their sources?
(c) (i) What is the structure difference between vegetable oil and vegetable fat?
(ii)Describe how vegetable oil can be converted to soaps
(iii)Calculate the mass of the soap that will be obtained from 1kilogram of palmitin once is treated
with sodium hydroxide given that the reaction yield is 95%.What is the mass of the residue of this
reaction.
Determine the required quantity of sodium hydroxide to effect this transformation.
(iv)Discus the properties of a soap in cleaning action.
(v)Compare a soap and a detergent
(vi)Discus the advantages of synthetic detergents over soaps.
150
CHAP XIV: CARBOHYDRATES
XIV.1 Introduction and definition
Carbohydrate, any of a large group of compounds in which hydrogen and oxygen, in the proportions in which they
exist in water, are combined with carbon; the formula of most of these compounds may be expressed as Cm(H2O)n.
Structurally, however, these compounds are not hydrates of carbon, as the formula would seem to indicate.
Carbohydrates, as a class, are the most abundant organic compounds found in nature and are produced by green
plants and by bacteria using the process known as photosynthesis, in which carbon dioxide is taken from the air by
means of solar energy to yield the carbohydrates as well as all the other chemicals needed by the organisms to survive
and grow.
The carbohydrate group consists principally of sugar, starch, dextrin, cellulose, and glycogen, substances that
constitute an important part of the human diet and that of many animals.
The simplest of them are the simple sugars, or monosaccharide, which contains either an aldehydes or a ketone group
and the most important are glucose and fructose respectively.
Two monosaccharide molecules joined together by an oxygen atom, with the elimination of a molecule of water,
yield a disaccharide, of which the most important are sucrose (ordinary cane sugar), lactose, and maltose.
Polysaccharides have enormous molecules made up of one type or several types of monosaccharide units about 10 in
glycogen, for example; 25 in starch; and 100 to 200 in cellulose.
Carbohydrate Molecular formula Hydrate formula

Glucose and fructose C6H12O6 C6 (H2O)6
Sucrose C12H22O11 C12(H2O)11
Starch [C6H10O5]n [C6 (H2O)5]n
Within living organisms, carbohydrates serve both essential structural and energy-storage functions. In plants,
cellulose and hemicelluloses are the main structural elements. In invertebrate animals, the polysaccharide chitin is the
main components of the exoskeletons of arthropods and in vertebrate animals, the cell coatings of connective tissues
contain carbohydrates. Cell membranes are rich in glycoproteins, and so forth. Plants use starch and animals use
glycogen to store energy; when the energy is needed, the carbohydrates are broken down by enzymes (see the course
of biology for animal physiology in senior 6).
Briefly, carbohydrates are polyhydroxyl aldehydes or polyhydroxyl ketones or organic compounds that are derived
from, or that can be hydrolyzed to, polyhydroxyl aldehydes or polyhydroxyl ketones. Carbohydrates that have
aldehydes groups are called aldoses and those with ketone groups, ketoses. Carbohydrates with five-carbon atom
molecules are pentoses (deoxyribose, ribose) and those with six-carbon atom molecules are hexoses (glucose,
fructose, galactose).
XIV.2 Nomenclature and isomerism
Carbohydrates that have aldehydes groups are called aldoses and those with ketone groups, ketoses. During
assigning number for determining absolute configuration of chiral centre i.e. hydroxylated carbon with 4
different groups so called asymmetric carbon, aldehydes receive number 1while in ketose carbonyl group is
number two.
151
The most preferred representation of aldoses and ketoses further more carbohydrates in general are Fischer
and Haworth representation (cyclic representation). Some aldoses and ketoses are below presented:
CHO
CHO CHO
CHO CHO
H OH HO H H OH
HO H
H OH H OH
H OH HO H
H OH H OH H OH
CH2OH
CH2OH H OH
H OH H OH
L-Glyceraldehyde CH2OH
CH2OH CH2OH
D-Glyceraldehyde
D- D- D-
Allose Altrose Glucose
Aldotriose
Aldehyde groups
CHO CHO CHO

CHO CHO
H OH HO H H OH
HO H HO H
H OH HO H
HO H HO H
H OH HO H HO H
H OH HO H
H OH H OH H OH
H OH H OH
CH2OH CH2OH CH2OH
CH2OH CH2OH
D-Ribose D-Manose D-Idose D-Galactose D-Tallose
pentose
Hexoses
ALDOSES
152
Ketone groups 1CH2OH
2 O
CH2OH
3
HO H
CH2OH
O 4
H OH
O
HO H 5
H OH
CH2OH
CH2OH
6CH OH
Dihydroxacetone L-Erytrulose 2
D-Fructose
Ketoses
Glyceraldehydes exist as a pair of enantiomers that can be distinguished experimentally by their action on
polarized light. Enantiomers are streoisomers that are related like a right and left hand; one is the non-
superimposable mirror image of the other. Enantiomers are optically active because one isomer rotates the
plane of polarized light to the right (clockwise) and is said to be dextrorotatory designated by (+) more
generally D-(+) while the other isomer rotates the plane of the polarized light to the left (counterclockwise)
and is the levorotatory designated by (-) more generally L-(-).
Note: (i)Most organic compounds that exhibit optically activity have one or more carbon atoms with four
different groups attached and such substituted carbon atom is called a chiral carbon atom designated as C*.
e.g.: Let consider the structure of glyceraldehydes and glucose
CHO
H * OH
2CHO
HO * H
1
4H C* OH
H * OH
3CHOH
2
H * OH
D-(+)Glyceraldehyde
CH2OH
OneC*
D-(+)Glucose
2Enantiomers 4C*
24 Enantiomersor8enantiomerspair
(ii) The arrangement of the four groups about a chiral carbon is called its absolute configuration. The Fischer
projection of glyceraldehydes has the carbon atom chain vertically and places the most oxidized
group(CHO) at the top and the least oxidized group(CH2OH) at the bottom. The H and OH are written to the
sides, which leads to 2 possible structures.
153
mirror
CHO CHO
H OH HO H
CH2OH CH2OH
D-(+)Glyceraldehyde L-(-)Glyceraldehyde
Enantiomer pairs or antipodes

The R- and S-configuration is the most used for aldoses and ketoses nomenclature in order to distinguish optical
isomers since they have different configuration.
1 CHO
CHO
H 2 OH
H * OH
3
HO H
HO * H
4
HO H
H * OH
5
H OH
H * OH D-
6CH2OH
CH2OH
D-(+) (2R, 3S, 4S, 5R) Galactose
D-(+)(2R, 3S, 4R, 5R)- Glucose
Note: Determination of absolute configuration consists of 3 steps:

• Assign priority each substituent of the asymmetric carbon C* starting by 1 to 4 according to their
atomic number.
• Define the rotation direction of the four substituent if the priority 1 is on top(head of FISCHER and
the lowest priority 4 on bottom: foot of FISCHER) and the others are on left and right hand
position randomly let 2-3 or 3-2.
• If the rotation direction is from 1-2-4-3 is in clockwise(more generally 1-2-3 by omitting 4), the
absolute configuration is R(Latin: Rectus) while in counterclockwise is S-configuration(S:senester
in Latin language).This can be summarized as follow:
1 1
3 2 2 3
4 4
R S
154
O
H
C 2
1 OH
1 O
4
H C* OH permutation
3
HOH2C C C
H C OH 3 H
H
4
H
R-Configuration
mirror
1 OH 1 OH
2
H3C C* COOH HOOC C* CH3
3 2 3
H H
4 4
R-Configuration S-Configuration
Enantiomer pairs of Lactic acid

Note: In case the highest priority is not on top but on equatorial planes(hands), determine rotation direction
and then after absolute configuration; the real configuration is the inverse of the above determined
configuration without dealing of permutation. But in case the highest priority is on bottom and lowest on
top, the real configuration after a rotation of 1800 remains.
Activity 1: Discus all optical isomers of D-Threose of formula is given without FISCHER projection in two
dimension HOCH2-CHOH-CHOH-CHO and determine their absolute configuration.
2.1. CYCLIC STRUCTURE
Although we have represented monosaccharide as straight- chain structures, most exist mainly in cyclic forms. For
example, less than 0.02% of D-(+) Glucose exist in solution in straight-chain form. In glucose, the OH group on the
fifth carbon designated C-5 adds to the carbonyl carbonyl C-1 after reacting with water, forming a ring with five C
atoms and one Oxygen atom.
Ring closure results in a new OH group that can extend up from the ring or down below the ring and makes C-1 a
new chiral carbon center; therefore, there are two cyclic forms of D-(+) glucose. The form in which the OH extends
downward is designated α -D-glucose and that with the OH pointing up is β-glucose.
155
OH
1 CHO OH
H OH 1
2 H
H * OH 1C
2
3 2 H OH
H * OH
H * H
O 3
H2O 3 HO H O
4 HO * H
H * OH
4 4
5 H OH
H * OH
H * OH
5
5 H
6CH OH H * OH
2
6 CH OH 6 CH2OH
D-(+) Glucose 2
6 CH OH
6 CH2OH 2
5 O
5 O
H H
H OH
H
H OH
H 1
1 Or 4
4
H O OH H
OH H OH OH
HO OH H
HO H
H 2 3 2
OH
3
H OH H OH
H OH
B-D-Glucopyranose a- D Glucopyranose
Note: This cyclic representation is known as Haworth representation which place convert a FISCHER representation
of a simple carbohydrate to ring within consideration left-OH will be down oriented while right- OH are up oriented
from.
The same as glucose, we can represent fructose in Haworth form:
6CH OH O OH
2
6 CH2OH O 1
CH2OH
5
2 5 2
H H HO CH2OH
1 H H HO OH
4 3 3
4
OH H
OH H
B-D-Fructofuranose
a-D-Fructofuranose
Activity 2: Try to draw HAWORTH representation of D-ribose, D-Lactose, D-Galactose and D-Idose and identify
chiral center in order to build a generalized conclusion relationship between Haworth and Fischer representation.
Two or more simple carbohydrate like glucose and fructose can be condensed with water elimination in order to form
disaccharides late on polysaccharide when the degree of polycondensation increases.
156
XIV.3 Physical and chemical properties
XIV.3.1 Physical properties
1. All simplest aldoses and ketoses are soluble in water, slightly soluble in alcohol and insoluble in organic
solvents.
2. In solution, they do not conduct electricity and even heat when they are in solid state.
3. At room temperature, they form powder or crystals and have high melting and boiling points due to a great
number of OH groups
4. Some are of good taste like fructose and sugar (sucrose) while others are less sweet (glucose) or do not like
starch, cellulose, maltose,
5. They rotate polarized light reason why they undergo mutarotation phenomena.
XIV.3.2 Chemical properties
The chemistry of carbohydrate whether simple or complex is complex to handle since they are natural
organic compounds that are metabolized, but in this section few of them will be studied.
1. Reduction: In the presence of catalyst like Ni or Pt aldoses and ketoses are reduced to polyols for
example glucose gives sorbitol.
CHO CH2OH
H OH H OH
HO H H2/Ni HO H
H OH H OH
H OH H OH
CH2OH CH2OH
D-Glucose
sorbitol
2. Condensation and polycondensation
(i) Condensation is process by which two function groups are combined together and water as a simple
and inorganic compound is eliminated. There fore, glucose can undergo condensation itself to
give maltose, with galactose to give lactose, with fructose to give sucrose.
O CH2OH
CH2OH CH2OH OH O
O CH2OH OH
O
OH
OH +
CH2OH -H2O
OH O
OH CH2O
OH OH OH H
OH
OH
a-D-Glucopyranose OH B-D-Fructofuranose
OH
a-1 4-B-fructo glucopyranoside
sucrose
157
6 CH2OH 6 CH2OH
CH2OH 5 5
CH2OH O O
O OH 1 4 OH 1
O 4
OH + OH
-H2O OH 3 2 O 3 2 OH
OH OH OH OH
OH OH
OH a1 4-glucopyranoside
OH
a-D-Glucopyranose a-D-Glucopyranose maltose(alpha form)
Activity 3: Lactose which is a milk sugar has a β-D galactose unit joined by C-1to 4 of α-D-glucose. Through
condensation process of the two aldohexoses in cyclic form can give lactose, give its mechanism.
By contrast, the acid hydrolysis of maltose give 2 glucose units, lactose give one unit of α-D-glucose and galactose in
β-form while sucrose give α-D-glucose and β-D-fructose.
Sucrose, a sugar with the formula C12H22011, belongs to the group of carbohydrates known as disaccharides. It is
soluble in water, slightly soluble in alcohol and ether, crystallizes in long, slender needles, and is dextrorotatory,
rotating the plane of polarized light to the right. Upon hydrolysis it yields a mixture of glucose and fructose, which
are levorotatory, turning the plane of polarized light to the left. Thus, the mixture obtained is known as invert sugar,
and the process is known as inversion. Inversion is carried on in the human intestine through the aid of the enzymes
known as invertase and sucrase. Sucrose is extracted chiefly from sugarcane and sugar beet and is commonly called
cane sugar. When heated to temperatures above 180° C (356° F), sucrose becomes the amorphous, brown, syrupy
substance called caramel.
Due to the fact that sucrose is dextrorotatory; of the products, glucose (dextrose) is also dextrorotatory but fructose
(levulose) is levorotatory for equal concentrations fructose rotates plane-polarized light much farther to the left than
glucose does to the right. Therefore when sucrose is hydrolyzed in solution, the optical rotation changes from (+) to (-
) and the process is known as the inversion of sucrose while the product, a mixture of glucose and fructose is known
as invert sugar.
(iii)Complex carbohydrates having more than ten monosaccharide units in a chain are called, starches.
• Starches, polymers of glucose are the principle energy storage materials of plants especially cereal grains
and potatoes. A simple starch called amylose has roughly 60 to300 glucose units joined C-1of one unit to C-
4 of next through α-linkage just as in the disaccharide maltose.
• Amylopectin has an amylose like chain structure but with branching on the chains C-1 toC-6 after 25 units
of glucose.
Starch is almost insoluble in cold water and in alcohol, but with boiling water it gives a colloidal suspension that may
form a jelly on cooling. Hot water changes starch slowly into smaller molecules called dextrins. This reaction, an
example of hydrolysis, is catalyzed by acids and by some enzymes. Dextrins, like starch, react with water, giving still
simpler molecules, the ultimate products being maltose, C12H22O11, a disaccharide, and glucose, C6H 12O6, a
monosaccharide when maltase enzyme is available .
Animals store glucose in the form of glycogen, a high molecular mass polysaccharide with even more chain
branching than amylopectin. Glycogen is stored in animal muscle and liver cells and can be converted back to
glucose as needed for energy.
• Lactose, sugar with formula C12H22O11, present in milk. Lactose is obtained from milk in the form of hard,
gritty crystals of composition C12H22O11·H2O, by evaporation of the whey remaining after removal of the fat
and precipitation of the casein. The crystals lose their water when heated to 140° C (284° F) and melt and
decompose at 202° C (396° F). Upon hydrolysis, lactose gives glucose and galactose. In the presence of the
proper enzymes it ferments into lactic acid(CH3-CHOH-COOH) and butanoic acid(CH3-CH2-CH2-COOH).
158
Lactose is less sweet than sucrose, rotates the plane of polarized light to the right (dextro-rotatory), and is
less soluble in water than either sucrose or glucose. It is important in the diet of young mammals and is often
added to baby foods; it is also used in confections and pharmaceutical tablets.
• Cellulose (Latin cellula, “little cell”), complex carbohydrate, the chief constituent of the cell wall of all plant
cells. In plants, cellulose is normally combined with woody, fatty, or gummy substances. Microorganisms in
the digestive tracts of herbivorous animals break down the cellulose into products that can then be absorbed.
Cellulose is insoluble in all ordinary solvents and may be readily separated from the other constituents of plants.
Depending on its concentration, sulfuric acid acts on cellulose to produce glucose, soluble starch, or amyloid; the last
is a form of starch used for the coating of parchment paper.
When cellulose is treated with an alkali and then exposed to the fumes of carbon disulfide, the solution yields films
and threads. Rayon and cellophane are cellulose regenerated from such solutions. Cellulose acetates are spun into fine
filaments for the manufacture of some fabrics and are also used for photographic safety film, as a substitute for glass,
for the manufacture of safety glass, and as a molding material. Cellulose ethers are used in paper sizings, adhesives,
soaps, and synthetic resins.
With mixtures of nitric and sulfuric acids, cellulose forms a series of flammable and explosive compounds known as
cellulose nitrates, or nitrocelluloses. Pyroxylin, also called collodion cotton, is a nitrate used in various lacquers and
plastics; another, collodion, is used in medicine, photography, and the manufacture of artificial leather and some
lacquers. A third nitrate, guncotton, is a high explosive.
Activity 4: Explain why humans like most animals can not use cellulose as energy source but most ruminants (goats,
sheep and cow) can use cellulose taken from glasses as food energy source.
3. Oxidation of simple aldoses deal with alcohol group (-OH) whether primary or secondary and aldehydes
group to carboxylic according to the strength of the oxidizing agents.
(i) Glucose is oxidized by specific enzyme to α-D-glucuronic acid which interacts with exogenic and
endogenic substance and tight them in order to give conjugated β-D-glucuronic derivatives that
are most soluble and allow its excretion from internal system because it detoxifies poisons.
159
carboxylic
primary
group
alcohol
COOH
CH2OH
O
O
Enzyme
OH OH
OH OH OH
OH
OH
OH
a-D-glucuronic acid
Glucose
(ii) Nitric acid oxidizes both primary alcohol and aldehydes group to carboxylic acid group.
aldehyde carboxylic group
CHO COOH
H OH H OH
HNO3 HO H
HO H secondary alcohols
do not change
H OH H OH
H OH H OH
CH2OH COOH
primary carboxylic group

alcohol
(iii) Periodic acid HIO4 oxidizes both aldehydes and secondary alcohols to formic acid while primary
alcohol is oxidized to formol, of course this reaction breaks down aldoses
aldehyde
CHO
O
H OH
HIO4 5
HO H H OH
Formic acid
H OH
+
H OH
H
CH2 OH 1
O
H
primary
alcohol Formol
(iv) Fehling solution and Tollens’reagent (silver nitrate in ammonia) oxidizes aldoses, therefore they are
called reducing carbohydrates. This reaction is used to characterize or to test reducing sugar
and non-reducing sugars. These are similar to aldehydes identification through qualitative
analyses.
(v) Phenylhydrazine reacts at room temperature with simple ketoses or aldoses as well as carbonyl
derivatives to give phenylhydrazones which forms yellow-orange precipitate.
160
By contrast, under heat conditions, 3 plausible reactions were recognized:
• Firstly, there is copondensation reaction between aldose and phenyl hydrazine to give phenylhydrazone,
• The second molecule oxidizes the secondary alcohol in position 2 from carbonyl group or primary alcohol
(carbon in position 1) in case of ketoses to ketone while phenyl hydrazine is reduced to aniline and
ammonia.
• The third molecule of phenylhydrazine undergoes condensation with carbonyl group resulting from the
action of the second molecule of phenylhydrazine. The final product after heating is an aldosazone or
ketosazone.
CHO H N
NH
C H N
C NH
H OH
H OH
O
HO HC
6H5NHNH2 HO H HO H
H OH warm
H OH H OH
H OH H OH
H OH
CH2OH
CH2OH
CH2OH
C6H5NH-NH2
Glucose Phenylhydrazone
H N NH
C
N
N HO H
H
H OH
H OH
CH2OH
Glucosazone
4. Kiliani-Fischer synthesis allow us to produce a mixture of 2 aldoses of (n+1) C from aldoses with n C
through the reaction of aldoses with HCN/NaCN as well as discussed in aldehydes section.
CN H O
COOH C
H C OH
H C OH H C OH
HO H
H
O
HO H
H2/Ni
HO H
C H OH
H2O
+ H OH
H H OH
HO H H OH
HCN H OH H OH
H OH CH2OH
NaCN CH2OH CH2OH
H OH
D-Glucose
CN
CH2OH
COOH O
D-Arabinose HO C H H
C
HO C H
HO H H2O H2/Ni HO C H
H OH H+ HO H
HO H
H OH
H OH
H OH
H OH
CH2OH
H OH
CH2OH
CH2OH
D-Mannose
161
Note: Wohl degradation is the inverse process of Kiliani-Fischer synthesis since it effects the
preparation of an aldose of (n-1)C from n C via cyanidation process using hydroxylamine in order to
form oxime which reacts with ethanoic anhydride in order to esterify each alcohol group in the aldoses
and then dehydrated to nitriles with react with Ag2O to give aldoses with (n-1)C and AgCN.
XIV.4. Carbohydrate preparations
• The main preparation of carbohydrates is extraction method from plants and other natural resources of
storage.
• Carbohydrates, as a class, are the most abundant organic compounds found in nature in complex structure of
simple aldoses and or ketoses by natural condensation process.
• They are produced by green plants and by bacteria using the process known as photosynthesis, in which
carbon dioxide is taken from the air (atmosphere) by means of solar energy to yield the carbohydrates as
well as all the other chemicals needed by the organisms to survive and grow.
• From the acid or catalyzed hydrolysis, complex carbohydrates like starch give disaccharides (maltose) which
using specific enzymes gives glucose unity to be storage as energy source.
• Another industrial process but difficult to perform due to regioselectivity and chiral issue, Kiliani-Fischer
and Wohl degradation can be effected according to the desired transformation.
XIV.5 USES
• Carbohydrates are used in the manufacture of fabrics, photographic film, plastics, and other products.
• Cellulose, a carbohydrate, can be converted into viscose rayon, acetate rayon, and paper products.
Nitrocellulose (cellulose nitrate) is used in the production of motion picture film, cement, guncotton,
celluloid, and similar kinds of plastics.
• Starch is used in the preparation of foods for livestock and humans; pectin, a jelling agent; gum arabic; and
agar, used in the production of adhesive materials, sizing materials, and emulsions. Gum arabic is also used
in demulcent medicines. Agar, a constituent of some laxatives, is also used as a thickening agent in food and
as a medium for bacterial culture.
• Hemicellulose is used to modify paper during its manufacture.
• The carbohydrate dextran is a polysaccharide used in medicine as a blood-plasma-volume expander to
counteract acute shock; another carbohydrate, heparin sulfate, is a blood anticoagulant.
• Glucose is chiefly used as a sweetening agent in the food-processing industries and it is also used in tanning,
in dye baths, in making tableted products, and in medicine for treating dehydration and for intravenous
feeding.
• They are in brew industry through fermentation process (see alcohol).
162
XIV.6.Exercises
1. The following structure A and B can have different isomers but let us focus our point of view about optical
isomers:
CHO CHO
H OH HO H
HO H H OH
HO H H OH
H OH HO H
CH2OH CH2OH
A B
(i) Recognize the class of these organic compounds and define the relationship between A and B.
(ii) Provide the correct and most complete name including absolute configuration of A and B.
(iii) Give the Haworth representation of both structures A and B including all possible isomers.
(iv) Give the products resulting from the reaction of A or B with:
a. Nitric acid
b. Periodic acid
c. Hydrogen in the presence of catalysts like Ni
d. Phenylhydrazine in excess
e. HCN+NaCN/H2O,H+
f. Wohl degradation
g. Fehling solution
h. –α-D-Glucopyranose
State whether the resulting products are meso or can rotate the polarized plane
(v) According to the conditions, it is possible to obtain two possible structure from A in crystal forms.
Identify these crystals.
If these crystals were dissolved in water their specific rotator coefficient is 150.70 and 52.80
respectively to their stability trends and after 10 minutes, the resulting solution were placed in a
polarimeter of 30cm as length and the specific rotator coefficient decrease slightly to 80.20. Discus
this behavior of A in solution
a. Calculate the percentage of each crystals in solution and state whether is it a racemic
mixture or not.
b. If 100 mg of A in crystals were dissolved in 50ml of water, calculate the deviation angle
that will be observed on the screen of a polarimeter or a connected detector of the
computer.
c. Explain the main source of D-galactose.
α = [α ]λ .C.l wher c is concentration in g/ml and l is the length of the tube in decimeter.
T
Hint: Biot’s law
2. An aldopentose A which belong to D-series react with nitric acid to form B that can not rotate the polarized
light. A through WOHL degradation give C which react with nitric acid to give E which of like
configuration (lk).
(i) Represent A, B, C, and E according to Fischer and HAWORTH and state whether E is optical
active. Note: If so, determine its absolute configuration.
(ii) Compare the absolute configuration of Haworth and Fischer projection
163
CHAP XV: AMINO ACIDS AND PROTEINS
XV.1 Introduction and definition
Amino Acids, important class of organic compounds that contain both the amino (-NH2) group and carboxyl (-
COOH) group. Hence, their general formula is
H2N HC COOH
Of these acids, 20 serve as the building blocks of proteins are known as the standard, or alpha, amino acids, they
comprise alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine,
isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.
XV.2 Nomenclature and isomerism
O
O
H2N CH C OH
H2 N CH C OH
CH3
H
glycine(Gly:G) Alanine(Ala :A)
NH2
NH2
HO C C C CH
H2 N C N C C C CH
H2 H2
H H2 H2 H2
O C O
NH C O
OH
OH
Arginine(Arg:R) Glutamic acid(Glu:E)
NH2
NH2
Methionine(Met:M)
H3 C CH C CH
H2
H3C S C C CH
CH3 C O H2 H2
C O
OH
Leucine(Leu:L) OH
164
OH
NH2
O C
H2 N C C C CH
H2 H2
CH C C C C NH2
O C O H2 H2 H2 H2
NH2
OH
Glutamine(Gln:Q) Lysine(Lys:K)
O NH2
O
Asparagine(Asn:N)
H2N CH C OH H2 N C C CH
H2N CH C OH H2
CH OH O C O
CH2
CH3 OH
OH
Threonine(Thr:T) Serine(Ser:S)
O
H2N CH C OH
NH2
CH2
Aspartic acid(Asp:D)
HO C C CH
H2
O C O
HN
OH
Tryptophane(Trp:W)
H2 N CH C OH
NH2
CH2
Phenylalanine(Phe:F)
NH2
Tyrosine(Tyr:Y)
C CH
H2
HO C CH
N C O H2
C O
NH OH
Histidine(His:H) OH
165
O
O
O H2N CH C OH O
C OH
H2N CH C OH CH CH3 H2N CH C OH
CH2 CH2 CH CH3

HN
SH CH3 CH3
Cysteine(Cys:C) Isoleucine(Ile:I) Proline(Pro:P) Valine(Val:V)
As the formula shows, the amino and carboxyl groups are both attached to a single carbon atom, which is called the
alpha carbon atom. Attached to the carbon atom is a variable group (R); it is in their R groups that the molecules of
the 20 standard amino acids differ from one another.
Due to the facts that α-amino acids are organic compounds containing two functional groups amine(-NH2), and
carboxylic acid group(-COOH) which takes priority during numbering, they can be named according to IUPAC as
already discussed(see acid).
For example, Alanine can be named as α-amino propanoic acid or 2-amino propanoic acid.
Our bodies are unable to synthesize certain of the amino acids needed to build functioning protein molecules; these
essential amino acids must be included in our diet. These are 8 amino acids tryptophan, isoleucine, lysine, leucine,
phenylalanine, threonine, methionine, valine and act as limitin reactants.
Note: If there is shortage of any of these building blocks, the body can’t make enough of the proper protein
molecules.
The isomers, in amino acid series may result from displacement of different functional groups like (-
COOH) and (-NH2) which can generate amide and other functional isomers.
A part from functional isomers, we have also optical isomers because all α-amino acids except glycine have at least
one asymmetric carbon C* or chiral carbon atom .
Note: All amino acids occur naturally as L-series which is also provided during protein test.
COOH
COOH COOH
C
H H2N H H NH2
NH2
R R R
L-amino acid D-amino acid
not found in proteins
166
All amino acids of L-series have (2S) as its absolute configuration except cysteine which is (2R) configuration.
Therefore seniority is from H2N, -CH2SH, -COOH, H since Sulfur takes priority to Oxygen and hence they are
optically active because they can rotate the polarized light.
Activity 1: Prove the validity of the above statement for all the amino acids
XV.3 Physical and chemical properties
XV.3.1Physical properties
1. Most amino acids occurs naturally in solid state due to enormous hydrogen bonding which enhance
intermolecular forces and maintain stronger interactions.
2. Amino acids have high melting point and boiling points due to hydrogen bonding
3. They are not volatile, but some colorless, odorless while others containing sulfur are yellow colored.
4. Amino acids are soluble in water but insoluble in organic solvents except phenylalanine and have the
density closed to the one of water which 1.00.
5. It is difficult to find a free aa but occurs combined in proteins as they storage system by our body.
XV.3.2 Chemical properties
a. Amino acids are amphoteric because they react either with acid as bases or with bases as acids.
In highly acid aqueous solutions( at lower pH closed to zero), the amino acid accept a proton H+ from the aqueous
acid and are Cations while in highly basic solutions(at higher pH closed to 14) , the amino acids donate a proton to
the aqueous base and are anions.
At some intermediate point, they exist as dipolar ions called Zwitterion as known as internal salt.
167
_
R CH COOH + H2O R CH COOH + HO
(I)
NH2 NH3 base

Base
acid +
acid
acid-base couple
_
CH R CH COO + H3O+
(II) R COOH + H2O
NH2 acid
NH2
Base
acid base
acid-base couple
From (I) and (II), amino acids are amphoteric
Therefore, they can undergo self protonation at the pH called isoelectric point noted as pI
R HC COOH R HC COO _
+
H2N H3N zwiterion
_
HO _ _ HO_ R CH COO
R CH COOH R CH COO
+ H+
H NH2
NH3+ NH3+
zwitterion
0 ACIDE 7 BASE 14
_ pH
R CH COOH R CH COO
pHi
NH3+ _ NH2
R CH COO
NH3+
zwitterion
From the above combined reactions, we remark that amino acids can act as buffer solutions what allow to our blood
to resist to pH changes if any amount of stronger acid or base is added because amino acids are dissolved in blood
as the main component of our body.
b. Condensation and polycondensation reaction
Amino acids can join together through an amide linkage by eliminating molecule of water. This process is known as
condensation.
168
In biochemistry, the amide linkage is known as a peptide linkage and the short chains of amino acid units are called
peptides. A dipeptide has two amino acids, tripeptide has three and so on; with a large number of amino acid units,
the molecule is called polypeptide.
Alanine glycine
serine
O O
H O
H2N CH C OH + N CH C OH + H2 N CH C OH
CH3 CH2
H H
OH
Alanyl Glycyl Seryl
O O O
H2N CH C HN CH C HN CH C OH + 2 H2O
CH3 H amide CH2

amide linkage
linkage OH
For example: Tripeptide: Ala-Gly-Ser
Note: Both extremities of the dipeptide can under condensation by creating a new amide linkage wich can be repeated
several time and produce a polypeptide if less than 50 amino acids while if aa are 50 or more, the molecule become a
protein.
Note: As discussed in biology, the primary structure of a protein is the exact sequence of amino acid units in the
protein molecule while secondary structure of a protein is the structure or shape of an entire protein chain which are α
–helix and the β-pleated sheet.
This is due to the fact that different sequences of the acids along a chain, however, affect the structure of a protein
molecule in different ways. Forces such as hydrogen bonds, disulfide bridges, attractions between positive and
negative charges, and hydrophobic “water-fearing”) and hydrophilic (“water-loving”) linkages cause a protein
molecule to coil or fold into a secondary structure, examples of which are the so-called alpha helix and the beta
pleated sheet. When forces cause the molecule to become even more compact, as in globular proteins, a tertiary
protein structure is formed. When a protein is made up of more than one polypeptide chain, as in hemoglobin and
some enzymes, it is said to have a quaternary structure.
169
Interactions between the molecules that make up a protein cause the coiled polypeptide chain (left) to fold into a
three-dimensional structure (center) which may join others to form a large, complex protein (right).
These 20 amino acids are involved in protein synthesis since once there is a slight change in polypeptide sequence
you obtain another molecule quite different to the first even if they have the same amino acids but different in
connectivity. These syntheses have been discussed in biology course and can be effected through genetic code
involving biochemical reaction.
Genetic Code
170
Messenger RNA (mRNA) is the template for protein synthesis. It consists of a series of nucleotides, each containing
one of four nitrogen bases: uracil (U), cytosine (C), adenine (A), and guanine (G). The order of nucleotides in a
strand of mRNA specifies the order in which amino acids are added as a protein is built. Each series of three
nucleotides specifies one amino acid. This chart identifies each amino acid by its three-letter codon (s). For example,
G under the “first letter” column, C under the “second letter” column, and A under the “third letter” column intersect
at alanine, the amino acid specified by the sequence GCA. Most amino acids are identified by more than one codon
(for instance, GCU, GCC, GCA, and GCG all encode alanine).
Note: If you want to know the number of amino acids combined in polypeptide structure, you can hydrolyze the
polypeptide or treat it using trifluoro acetic acid because amide linkage will be broken down in two fragments: one
with carboxylic group (-COOH) and on the other hand the amine (-NH2) group.
c. Acylation and esterification reaction in amino acid series
Amino acids reacts with anhydrides and acid chlorides to give N-acyl derivatives. This reaction is similar to amines
while carboxylic acid group can undergo esterification with saturated alcohols in the presence of fuming HCl or
paratoluene sulfonic acid(PTSA).
R
O
OH
Cl
NH
O
O
O O R
1.NaOH
OH
+ H2 N 2. HCl diluted
amino acidO
acid chloride
R
R
O
OH + H O H2N
H2N
O
amino acidO Phenol + H2O
d. Reaction of both groups: complex formation in amino acids formation
Amino acids react with transition metals like copper Cu2+ to give blue complexes in which the metals is attached to a
polyddentate ligand (chelating agent) via chelation process.
171
O
R
O
Cu(OAc)2
NH2 O
_
2 HO NH2 + 2 ACOH
2+
Cu
R
H2N
_
O
R
Cordination number is two
O
Notice: Sodium ethyle diamine tetracetate is used to decompose copper amino acid complexes in amino acid and
copper is there complexed with a polydentate EDTA which is more stable and can not be easily broken down or
dissociated.
XV.4 Preparation of amino acids
Most plants and microorganisms are able to use inorganic compounds to make all the amino acids they require for
normal growth. Animals, however, must obtain some of the standard amino acids from their diet in order to survive;
these particular amino acids are called essential. Essential amino acids for humans include lysine, tryptophan, valine,
histidine, leucine, isoleucine, phenylalanine, threonine, methionine, and arginine. They are found in adequate
amounts in protein-rich foods from animal sources or in carefully chosen combinations of plant proteins.
In addition to the amino acids that form proteins, more than 150 other amino acids have been found in nature,
including some that have the carboxyl and amino groups attached to separate carbon atoms. These unusually
structured amino acids are most often found in fungi and higher plants.
On the other hand the laboratory synthesis of amino acid can be effected from ethyl N-Acetylaminomalonate also
called ethyl acetamidomalonate by alkylation through 4 steps :
172
O COOCH2CH3 O COOCH2CH3
1)EtONa
2)R-X
H3C C HN C H H 3C C HN C R
COOCH2CH3 COOCH2CH3
1) 2NaOH
+
2) H
COOH O O COOH
H C NH C CH3 H3C C HN C R
Heating
R COOH
COOH
+
NH
H3C C C H
O R
Racemic mixture of N-Acetyl

amino acid Acylase COOH
H2N H L-Amino acids
Note: This process is not easy to handle since it may contain many isomers due to regioselectivity reaction that is
encountered here, however acylase enzyme is used to resolve such problem.
XV.5 Uses of amino acids.
• Amino acids are raw material in proteins (biopolymers or natural polymers) synthesis.
• The standard amino acids serve as raw materials for the manufacture of many other cellular products,
including hormones (see Hormone) and pigments.
• In addition, several of these amino acids are key intermediates in cellular metabolism (see Metabolism)
• Proteins resulting from amino acid polycondensation are powerful in human body growing and
• Proteins in the diet serve primarily to build and maintain cells, but their chemical breakdown also provides
energy, yielding close to the same 4 calories per gram as do carbohydrates (see Metabolism).
• Besides their function in growth and cell maintenance, proteins are also responsible for muscle contraction.
The digestive enzymes are proteins, as are insulin and most other hormones. The antibodies of the immune
system are proteins, and proteins such as hemoglobin carry vital substances throughout the body.
XV.6 Exercises
I. The threonine is an amino acid with the configuration 2S, 3R most encountered in most plant oil is used in proteins
synthesis.
(i) Represent the optic isomers of threonine and plot each according to Fischer projection
173
(ii) Plot the reaction of L-threonine with:
• NaOH
• HCl
• H2O
• PCl5
• Ethanol
• Acetic acid
• H2SO4, Conc.
• Alanine
II. Let A be the α- amino acid R-CH(NH2)-COOH with R an alkyl group to be determine late on.
(i) Write down the possible structures called the dipeptide P1 and P2 resulting from the reaction
between A and valine as one of the 20 amino acid.
(ii) Represent by cycling the peptide bond in both structures P1 and P2, and define their relationships.
(iii) Determine R if the laboratory test resulting from fragmentation of peptide recorder P1 and P2
molecular weight equal to 180g.mol-1.Hence recognize A.
(iv) Given that amino acid like A exist in solution in 3 different species according to the pH which
allow them to pass through cell membrane. Represent these forms according to pH .
(v) From the diagram plotted in (iv), define the zwitterions.
(vi) State which kinds of polymers will be obtained from A and valine several times.
(vii) Within comparison to nylon6,6, a polymer resulting from Adipic acid(HOOC-(CH2)4-COOH and
hexane-1,6-diamine, and the polymers in (vi), state their common points if exist and their
difference whatever in features.
Answer: R is CH3 therefore A is Alanine (Ala).
REFERENCES
174
1. John W.Hill and Ralph H.Petrucci (1999) General chemistry: an integrated approach; second edition
2. B.S.BAHL,G.D. Tuli et Arun BAHL(2000), Essential of Physical chemistry : S.Chand Campany Ltd, New
Delhi.
3. Peter.W.Atkins, (2000) Physical chemistry, sixth edition ; oxford
4. Philip. Mathews(2004) Advanced chemistry, Cambridge university
5. Armand COLLIN(2008), Advanced organic chemistry: course, eighth edition
6. Armand COLLIN(2008), Advanced organic chemistry: exercises, eighth edition
7. H.Galons (2007), chimie organique : l’essentiel du cours et exercices corrigés, deuxième édition
175

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CHEMISTRY COURSE FOR S5MCB&PCM&PCB

CHAP I: GENERAL INTRODUCTION TO ORGANIC CHEMISTRY

CHAP II: ALKANES ............................................................................................ 14

CHAP III: ALKENES .......................................................................................... 24

III.6 EXERCISES ............................................................................................................................... 36

CHAP IV: ALKYNES ........................................................................................... 37

CHAP V: PETROLEUM AND ITS ENGINEERING CHEMISTRY.................. 43

CHAP VI: ALKYL HALIDES .............................................................................. 51

INDEX NOTE ...................................................................................................... 59

VII.1 Introduction ............................................................................................................................... 63

CHAP VIII: ETHERS .......................................................................................... 81

CHAP IX: AMINES ............................................................................................. 86

CHAP X: CARBONYL COMPOUNDS: ALDEHYDES AND KETONES .......... 95

X. 4. ALDEHYDES AND KETONES PREPARATIONS ................................................................. 105

CHAP XI: CARBOXYLIC ACIDS ..................................................................... 112

CHAP XII: FUNCTIONAL DERIVATIVES OF CARBOXYLIC ACIDS ........ 124

ACID CHLORIDES ........................................................................................... 125

B.ESTERS .......................................................................................................... 127

C.5 Uses............................................................................................................................................ 133

D.ACID ANHYDRIDES ..................................................................................... 134

E .NITRILES ...................................................................................................... 137

EXERCISES ....................................................................................................... 140

REVIEW QUESTIONS ON LIPIDS.................................................................. 150

CHAP XIV: CARBOHYDRATES ...................................................................... 151

XIV.3.2 Chemical properties ......................................................................................................... 157

CHAP XV: AMINO ACIDS AND PROTEINS .................................................. 164

• Activities that are arranged by topics in subtopics in order to assess knowledge in

0.1 Application of organic chemistry

CHAP I: GENERAL INTRODUCTION TO ORGANIC CHEMISTRY CONCEPTS

I.1 Carbon background

Carbon atom is unique because of:

I.2. Functional groups

Table 1: Table of some organic functional groups

Exclusively Carbon Functional Groups

Alkene H2C=CH2 Ethene Ethylene

Alkyne HC≡CH Ethyne Acetylene

Arene C6H6 Benzene Benzene

Functional Groups with Single Bonds to Heteroatoms

Halide H3C-I Iodomethane Methyl iodide

Alcohol CH3CH2OH Ethanol Ethyl alcohol

Ether CH3CH2OCH2CH3 Diethyl ether Ether

Amine H3C-NH2 Aminomethane Methylamine

Nitro Compound H3C-NO2 Nitromethane

Thiol H3C-SH Methanethiol Methyl mercaptan

Sulfide H3C-S-CH3 Dimethyl sulfide

Functional Groups with Multiple Bonds to Heteroatoms

Nitrile H3C-CN Ethanenitrile Acetonitrile

Aldehyde H3CCHO Ethanal Acetaldehyde

Ketone H3CCOCH3 Propanone Acetone

Carboxylic Acid H3CCO2H Ethanoic Acid Acetic acid

Ester H3CCO2CH2CH3 Ethyl ethanoate Ethyl acetate

Acid Halide H3CCOCl Ethanoyl chloride Acetyl chloride

Acid Anhydride (H3CCO)2O Ethanoic anhydride Acetic anhydride

I.3. Empirical, Molecular and structural formulae

I.3. 2. Molecular formula

Vapour density =½molecular weight

molecula weight = 2*vapour density= 2*37.5= 75gr/mol

• Percentage of oxygen = 100-26.66-2.22=71.12%

• Volume of hydrocarbon reacting: 15cm3

Answer: (i) The molar mass is deduced from RAOULT’s law:

I.3.3. Structural formula

Table2: Table of different formulae used in organic chemistry molecular presentation

Molecular Condensed structural Structural formula Stick formula

molecula weight = 2vapour density= 237.5= 75gr/mol