Fully Compiled Chm102-1

CHM 102
INTRODUCTORY CHEMISTRY II
MODULE 1
INSTRUCTOR 1
DR. MRS L.M.DUROSINMI

COURSE OUTLINE
BRIEF INTRODUCTION TO
CHM 102 TOPICS
THEORY AND TECHNIQUES OF
QUALITATIVE INORGANIC ANALYSIS
Qualitative Inorganic Analysis:
• A method of analytical chemistry which seeks to
find elemental composition of inorganic
compounds through various reagents.
• Deals with careful detection of ions in
an aqueous solution.
• The solution is treated with various reagents to
test for reactions characteristic of certain ions,
which may cause color change, formation of ppt
or other visible changes.
PHYSICAL APPEARANCE OF
INORGANIC SALTS.
• Black -----
• MnO, MnO2, FeO, CuO, Co3O4, Ni2O3;
Also sulfides of Ag+, Cu+, Cu2+,Ni2+, Fe2+, Co2+,
Pb2+, Hg2+, Bi3+
• Blue------- Hydrated Cu2+ salts
• Red -------HgO, HgI2, Pb3O4
• Green ------Cr3+, Ni2+, hydrated Fe2+ salts
PHYSICAL APPEARANCE OF
INORGANIC SALTS, contd.
• Light Pink ------Hydrated Mn2+ salts

• Orange --- KO2, K2Cr2O7, Sb2S3, Ferrocyanide
• Reddish Pink----- Hydrated Co2+ salts.
• Yellow-------Chromates, AgBr, As2S3, AgI, PbI2,
CdS
• ----- CdO, Fe2O3, PbO2, CuCrO4
DETECTING CATIONS
• Cations are usually classified into six groups.
• Each group has a common reagent which can
be used to separate them from the solution.
• To obtain meaningful results, the separation is
done in sequence.
1st Group of Cations
• Most important cations in 1st group are Ag+, Hg2+ and Pb2+.
• The ions form insoluble chlorides. Thus, the group reagent to
separate them is hydrochloric acid. 1–2 M.
• Concentrated HCl must not be used, because it forms a soluble
complex ion ([PbCl4]2−) with Pb2+. Consequently, the Pb2+ ion
would go undetected.
• The chlorides of these elements cannot be distinguished from
each other by their colour - they are all white solid compounds.
But PbCl2 is soluble in hot water, and can therefore be
differentiated easily. Ammonia is used as a reagent to
distinguish between the other two. While AgCl dissolves in
ammonia (due to the formation of the complex ion
[Ag(NH3)2]+), Hg2Cl2 gives a black precipitate.
2nd Group of Cations
• These consists of ions that form acid-insoluble sulfides. The
Cations include: Cd2+, Bi3+, Cu2+, As3+, As5+, Sb3+, Sb5+, Sn2+,
Sn4+ and Hg2+. Pb2+.
• The reagent used is any substance that gives S2− ions in such
solutions; most commonly used are hydrogen sulfide (at 0.2-
0.3 M) in the presence of dilute HCl.
• CdS, is yellow. All the precipitates, except for HgS, are

soluble in dilute nitric acid. HgS is soluble only in aqua regia,
which can be used to separate it from the rest.
2nd Group of Cations
• The action of ammonia is also useful in differentiating

the cations. CuS dissolves in ammonia forming an
intense blue solution, whereas CdS dissolves forming a
colourless solution. The sulfides of As3+, As5+, Sb3+,
Sb5+, Sn2+, Sn4+ are soluble in yellow ammonium
sulfide, where they form polysulphide complexes.
•
• If it forms a yellow precipitate, then Cd2+ or Sn4+ is
present; or if it forms a brown precipitate, then
Sn2+ must be present; or if a red orange precipitate is
formed, then Sb3+ is present.
3rd Group of Cations
• This group of cations includes ions that form hydroxides

which are insoluble even at low concentrations.
• Cations : Fe2+, Fe3+, Al3+, and Cr3+.
• The group is determined by making a solution of the salt in

water and adding ammonium chloride and ammonium
hydroxide. Ammonium chloride is added to ensure low
concentration of hydroxide ions.
3rd Group of Cations, contd
• Formation of a reddish-brown precipitate indicates
Fe3+;
• a gelatinous white precipitate indicates Al3+; and
• a green precipitate indicates Cr3+ or Fe2+. These two

are distinguished by adding sodium hydroxide in
excess to the green precipitate. If the precipitate
dissolves, Cr3+ is indicated; otherwise, Fe2+ is
present.
4th Group of Cations
• These include Zn2+, Ni2+, Co2+, and Mn2+.
• Zinc salts are colourless, Manganese salts are faint
pink or colourless, and Nickel and cobalt salts may be
brightly coloured, often blue-green.
• The precipitate, washed in water is reacted with dilute
hydrochloric acid. This precipitates nickel salts, if any.
The supernatant liquid is filtered and reacted with
excess of NaOH. This precipitates any Manganese
salts. Hydrogen sulphide is passed through the liquid.
If a white pptcipitate forms, Zinc is present.
• ions in the 5th group are Ba2+, Ca2+, and Sr2+.
• Ions in 5th analytical group of cations form carbonates that are
insoluble in water.
• The reagent used is (NH4)2CO3 with a neutral or slightly basic
pH.
• All the cations in the previous groups are separated
beforehand, since many of them also form insoluble
carbonates.
• To distinguish between these ions, flame test colour s used.
• : barium gives a yellow-green flame,
• calcium gives brick red, and
• strontium, crimson red.
• Cations left after separating groups 1-5 are considered to be

in the sixth group.
• These are Mg2+, Li+, Na+ and K+.
• All the ions are distinguished by flame color:
• lithium gives a red flame, sodium gives bright yellow (even

in trace amounts), potassium gives violet, and magnesium,
colorless (although magnesium metal burns with a bright
white flame).
DETECTING ANIONS
1st Group of Anions
o consists of CO32− , HCO3−, CH3COO−, S2−, and NO−
o The reagent for Group 1 anions is dilute hydrochloric acid

(HCl) or dilute sulfuric acid (H2SO4).
•
o Carbonates give effervescence with dilute H2SO4 due to the
release of CO2, a colorless gas which turns limewater milky
due to formation of CaCO3 (carbonatation).
o The milkiness disappears on passing an excess of the gas

through the lime water, due to formation of Ca(HCO3)2.
•
1st Group of Anions, contd
• Sulfides give the rotten egg smell of H2S when
treated with dilute H2SO4. The presence of sulfide is
confirmed by adding lead(II) acetate paper, which
turns black due to the formation of PbS. Sulfides also
turn solutions of red sodium nitroprusside purple.
• Sulfites produce SO2 gas, which smells of burning
sulfur, when treated with dilute acid. They turn
acidified K2Cr2O7 from orange to green
• Nitrites give reddish-brown fumes of NO2 when
treated with dilute H2SO4. These fumes cause a
solution of potassium iodide (KI) and starch to turn
blue.
2nd Group of Anions
• The 2nd group of anions consist of Cl−, Br−, I−, NO−
• The group reagent for Group 2 anion is concentrated

sulphuric acid (H2SO4).
• After addition of the acid, chlorides, bromides and
iodides form precipitates with silver nitrate. The
precipitates are white, pale yellow, and yellow,
respectively. The silver halides formed are completely
soluble, partially soluble, or not soluble at all,
respectively, in aqueous ammonia solution.
2nd Group of Anions, contd
• Chlorides are confirmed by the chromyl chloride test. When the
salt is heated with K2Cr2O7 and concentrated H2SO4, red
vapours of chromyl chloride (CrO2Cl2) are produced. Passing
this gas through a solution of NaOH produces a yellow solution
of Na2CrO4. The acidified solution of Na2CrO4 gives a yellow
precipitate with the addition of (CH3COO)2Pb.
• Bromides and iodides are confirmed by the layer test. A sodium

carbonate extract is made from the solution containing bromide
or iodide, and CHCl3 or CS
2 is added to the solution, which separates into two layers: an
orange colour in the CHCl
3 or CS
2 layer indicates the presence of Br−, and a violet colour
indicates the presence of I−.
• Nitrates give brown fumes with concentrated H2SO4 due to
formation of NO2.
3rd Group of Anions
• The anions consist of SO42− , Phosphate and borate anions;
• They react neither with concentrated nor diluted H2SO4.
• Sulfates give a white precipitate of BaSO4 with BaCl2 which

is insoluble in any acid or base.
• Phosphates give a yellow crystalline precipitate upon

addition of HNO3 and ammonium molybdate.
• Borates give a green flame characteristic of ethyl

borate when ignited with concentrated H2SO4 and ethanol.
MODULE 2
INSTRUCTOR 1
 Chemical bonding is one of the most basic fundamentals of
chemistry that explains other concepts such as molecules and
reactions.
 Everything in the world around us is made up of atoms, which
are tiny pieces of matter.
 The different atoms stick together to form all kinds of things in
the world..
 The atoms stick together because of chemical attraction.
 The attraction is created because of the electrostatic force
caused by the attraction between electrons and nuclei.
 To understand the concept of bonding, you must first know the
basics :
i. HOW atoms combine to form molecules?
ii. WHY do atoms form bonds?
iii. Why is sodium chloride a solid at room temp (mpt=801℃)
whereas hydrogen chloride is gas (mpt=−115℃).
iv. Why does sodium combine so vigorously with chlorine gas
but not at all with argon gas?
 To answer these questions, some fundamental points about
chemical bonding need to be established.
The basic answer is that atoms are trying to attain the
most stable (lowest-energy) state that they can.
 Many atoms become stable when their valence shell is

filled with electrons or when they satisfy the octet rule
(by having eight valence electrons).
 The atoms do so by gaining, losing, or sharing

electrons via bonds.
 The noble gases were the only elements whose
atoms seemed unable to form bonds to one
another or other atoms.
 Atoms of the noble gases do not normally
combine with any other metal.

 The lack of reactivity of these noble gases is
due to the fact that they already have low

energy.
 The low energy is associated with the atoms having a
complete outer shell of electrons.
 It is important to note that a molecule will only be

formed if it is more stable and has a lower energy
than individual atoms.

 What are Chemical Bonds?
 Chemical bonds are attractive forces that hold/bind

atoms together in form of molecules/compounds.
 Chemical bonds form because they lower the potential energy

between the charged particles that compose the atom.
Between 1916 & 1919, several important proposals about
chemical bonding were made by 3 scientists:
2 Americans – G.N. Lewis & Irving Langmuir

1 German – Walter Kossel.
THE PROPOSALS
 (1) That, there must be something unique in the
electronic configuration of inert gas atoms which
prevents their combination with other atoms,
 (2) That other atoms unite with one another so as to
acquire electronic configuration like the inert gas atoms.
 The theory that developed around these models/proposal became
most closely associated with Lewis theory.
LEWIS THEORY,
 By Lewis theory, the following basic ideas/points could be
developed:
1. Electrons, especially those of the outermost (i.e. Valence)
electronic shell, play a fundamental role in chemical bonding;
2. In some cases, chemical bonding results from the transfer of one or
more electrons from one atom to another. This leads to the
formation of positive and negative ions and a bond type called
ionic.
3. In other cases, chemical bonding involves the sharing of
electrons between atoms. This leads to formation of
molecules having a bond type called covalent.
4. Electrons are transferred or shared to the extent that each

atom acquires an especially stable electron configuration
such as that of a noble gas i.e. having eight outer-shell
electrons called an OCTET configuration.
The Octet rule is very reliable & very useful in explaining
a number of bonds formed in simple cases. It however
gives no indication of the shape adopted by the molecules.
CHEMICAL BONDING
MODULE 2
INSTRUCTOR 1
TYPES OF CHEMICAL BONDS
The type of chemical bond formed varies in strength and

properties. There are various types of chemical bonds
which are formed by atoms or molecules to give
compounds. These types of chemical bonds include:
 Ionic Bonds
 Covalent Bonds
 Coordinate covalent or Dative Bonds.
 Hydrogen Bonds
These types of bonds in chemical bonding are

formed from either the loss, gain, or sharing of
electrons between two atoms/molecules.
IONIC BOND
• This is formed when a metal atom transfers one or
more electrons to a non-metal atom.
• As a result of this transfer, the metal atom
becomes a positively charged ion (a cation) and
the non-metal, a negatively charged ion (anion).
IONIC BOND
IONIC BOND
In the diagram,
 Sodium transfers one of its valence electrons
to chlorine, resulting in formation of a sodium
ion with no electrons in its 3n shell and having
a full 2n shell;
 The chloride ion gains the one electron to
have eight electrons in its 3n shell, thereby
giving the chloride ion a stable octet.
IONIC BONDS
• Ionic solids are generally characterized by high

melting and boiling points along with brittle,
crystalline structures
• Generally ionic bond is the strongest chemical
bond because ionic bond forms a crystal lattice
structure which are attracted by strong
electrostatic force of attraction
COVALENT BONDING
• Covalent bonds are a class of chemical bonds

where valence electrons are shared between two
atoms, typically two non-metals.
• Formation of a covalent bond allows the non-
metals to obey the octet rule and thus become
more stable.
• The non-metals share electron density to form
strong bonding interactions.
• Covalent compounds typically have lower
melting and boiling points than ionic compounds.
COVALENT BONDS, CONTD
• Covalent bonds can be single, double, and
triple bonds;
• Covalent bonding requires a specific
orientation between atoms in order to achieve
the overlap between bonding orbitals.
• Covalent bonding interactions include sigma-
bonding (σ) and pi-bonding (π).
• Sigma bonds are the strongest type of covalent
interaction and are formed via the overlap of
atomic orbitals along the orbital axis.
The overlapped orbitals allow the shared
electrons to move freely between atoms.
Pi bonds are a weaker type of covalent

interactions and result from the overlap of
two lobes of the interacting atomic orbitals
above and below the orbital axis.
CHEMICAL BONDING
MODULE 3
INSTRUCTOR 1
POLAR COVALENT BOND
• Polar covalent bond is a separation of electric charge

in a covalent bond involving a shift of electrons
toward the atom with the more negative electron
affinity;
• A bond that results from unequal sharing of electrons.

• Unequal sharing due to the differences in the
electronegativity values of the two atoms.
For example:
H+  Cl-
POLAR COVALENT BOND
• Another example of such polar molecule is water.

• The covalent bonds between hydrogen and
oxygen atoms in water are polar covalent bonds.
• The shared electrons spend more time near the
oxygen nucleus, giving it a small negative charge,
than they spend near the hydrogen nuclei, thereby
giving the hydrogen atoms small positive charges.
POLAR COVALENT BOND
COORDINATE COVALENT BOND
• Formed when the lone or non-bonding pairs of

electrons in an atom takes part in a form of bonding.
• The two electrons being shared by the two atoms are
supplied by only one of the participating atoms.
• For the bond to be formed, the atom accepting the
electron must have empty orbital to accommodate the
two electrons.
A: B  +A:B-
Donor Acceptor
• Example:
• The bond between ammonia, (NH3) &
hydrogen ion, (H+) to give ammonium (NH4+).
• Nitrogen contributes the two electrons needed
to bond with hydrogen and therefore form the
ammonium ion with a Coordinate or dative
bond.
EXCEPTIONS TO THE OCTET RULE
a) Odd-Electron species
b) Incomplete octets
c) Expanded octets
Odd-Electron species
In odd-electron species, there is:
i. At least one unpaired electron in the structure.

ii. At least one atom lacks a complete octet of electrons.
The presence of unpaired electrons causes odd

electron species to be paramagnetic. For example,
NO is paramagnetic.
• The NO molecule has 11 valence electrons.

Nitrogen, N has 5 and Oxygen, O has six, 6.
This is an odd number. It therefore has an unpaired
electron
• This makes it to be paramagnetic
INCOMPLETE OCTETS
• The central atom has incomplete Octet,

• Example is Boron atom in Boron trifluoride.
• The number of electrons around the boron
atom is 6. Three from boron and three from the
3 fluorine atoms.
INCOMPLETE OCTETS
INCOMPLETE OCTETS
• BF3 readily combines with ammonia, NH3 to

form H3N.BF3 in order to complete the octet
configuration.
• The nitrogen donates both electrons to the
boron-nitrogen bond to form a coordinate
covalent bond
INCOMPLETE OCTETS
CHEMICAL BONDING
MODULE 4
INSTRUCTOR 1
EXCEPTIONS TO THE OCTET RULE, contd
EXPANDED OCTETS
• Phosphorus in group V with five electrons in the

valence shell forms two chlorides, PCl3 and PCl5
• For the PCl3, the number of outer electrons around
the central Phosphorous atom is eight, (octet), six from
the three covalent bonds with the chlorine atoms and
one lone pair of electrons.
EXPANDED OCTETS, contd
• In PCL5 , all the 5Cl atoms are bonded to the central

phosphorous atom through covalent bonds. This makes
a total of ten electrons surrounding the outer shell of
phosphorous.
• Therefore, expansion of the octet configuration.
• This is possible due to the availability of empty 3d
orbital in phosphorous to accommodate the excess
electrons.
• The phenomenon of octet expansion are found

in elements in the 3rd or higher periods of the
periodic table.
RESONANCE IN CHEMICAL BONDING
• There are molecules and ions for which

drawing a single Lewis structure is not
possible but an hybrid structure.
 Resonance is a phenomenon in which more
than one possible structures can be written for
a specie. That is, a situation where a true, one
single structure cannot be written.
RESONANCE IN CHEMICAL BONDING, contd
• Oxygen gas commonly occurs as diatomic

molecules. But it can also exist as triatomic
molecules, O3 called ozone.
• O2 molecule has an even number of electrons
(12). Thus it is expected to be a diamagnetic
molecule. But O2 molecule is paramagnetic
therefore the O2 molecule must have unpaired
electrons.
• Ozone, O3, is one such substances for which a

single valence-bond structure does not provide a
completely satisfactory representation of the
properties of the substance.
• Spectroscopic studies of ozone show that the
molecule has a bond angle of 117° at the
central oxygen atom, and each of the two
oxygen-oxygen bond lengths is 128 pm. :
• Experimental evidence indicates that the two

O-O bonds are the same and the measured
bond lengths showed that they are
intermediate between the values for a single
and double bond.
• Each bond length is 128pm (10-12 m)
• O-O-145pm
• O=O 121pm.
• Ozone -Triatomic molecule. There are two

possibilities.
•
• The arrows in this formula indicate that the

double bond and the single bond can change
places.
• The structure with a double bond in one
position and a single bond in the other does not
represent any state of the ozone molecule, but
the two structures together ,
• The experiment shows, however, that the two
bonds are identical.
• Therefore neither of the two structures can be

correct.
• One of the bonding pairs in ozone is spread
over the region of all three atoms rather than
localized on a particular oxygen-oxygen bond.
• This delocalized bonding is a type of chemical
bonding in which bonding pair of electrons are
spread over a number of atoms rather than
localized between two.
• This is called the resonance hybrid of the two

structures. It has unpaired electrons and thus
conforms to the experimentally measured
bond length in oxygen which shows it to have
some multiple bond character but in between
O-O and O=O.
CHEMICAL BONDING
MODULE 5
INSTRUCTOR 1
THE VALENCE BOND THEORY
The theory:
 Describes a chemical bond as the overlap of atomic orbitals.

 That the Covalent bond is a region of high electron charge
density (high electron probability) that results from the overlap
of atomic orbitals between two atoms.
 That most of the electrons retain essentially the same orbital
locations as in separate atoms and the bonding electrons are
localized (fixed) in the region of atomic orbital overlap.
The electrons move about both atoms and

gives both atoms access to two electrons;
they become a stable H2 molecule joined by
a single covalent bond.
 At some point, the electron charge clouds of the atoms begin
to merge.
 However, the two atoms cannot be brought too

closely because the atomic nuclei would
strongly repel one another and the bond would
become unstable.
 The greater the amount of overlap between the
two orbitals, the stronger the bond.
• Valence bond (VB) theory is one of two

basic theories—along with molecular
orbital (MO) theory—that use quantum
mechanics to explain chemical bonding.
VALENCE SHELL ELECTRON-PAIR
REPULSION (VSEPR) THEORY
• This theory focuses on pairs of electrons in the

outermost (valence) electronic shell.
• Electron pair, whether they are in chemical
bonds (bond pairs) or unshared (lone pairs)
repel one another.
• The electron pairs thus assume orientations in
space to minimize these repulsions.
VALENCE SHELL ELECTRON-PAIR
REPULSION (VSEPR) THEORY
• This tendency to minimize repulsions

between electron pairs causes chemical
bonds from a central atom to assume
certain orientations.
• This lead to particular geometrical shapes
for molecules
• The strength of electron pair repulsions
differs.
VSEPR THEORY
• The repulsion between two lone pairs is

greater than the repulsion between a lone
pair and a bond pair.
• Presence of a lone pair on the central atom
causes slight distortion of the bond angles
from their ideal values.
VSEPR THEORY
• Valence Shell Electron Pair Repulsion
(VSEPR) method helps one to determine the
shape of a substance without using high
technology methods such as X-ray
crystallography, NMR Spectroscopy, or
electron microscopy.
• Some of the most common shapes that can be
taken are linear, trigonal planar, tetrahedral,
pyramidal, and angular (or bent).
VSEPR THEORY
PREDICTING SHAPES OF MOLECULES
Methane, Ammonia and Water

Considering methane, CH4
• The VSEPR theory predicts that CH4 should be a
tetrahedral molecule with a carbon atom at the
center of the tetrahedron and H atoms at the
corner.
• This structure agrees with that established by
experimental evidence.
VSEPR THEORY
VSEPR THEORY
VSEPR THEORY
• Water, H2O
VSEPR THEORY
The charge cloud of the lone pair electrons spreads

out and forced the bonding electron pairs closer
together, thus reducing bond angles for .
Ammonia 107
Water 104.5
VSEPR THEORY
• The shape of a molecule or ion is governed by

the arrangement of the electron pairs around
the central atom.
• To predict the shape of the molecules, first
draw out the Lewis structure of the molecule.
• On the Lewis diagram, identify the central
atom. For example, for the molecule [PF6] -
the central atom is Phosphorus (P).
VSEPR THEORY
VSEPR Rules:
1. Identify the central atom
2. Count its valence electrons
3. Add one electron for each bonding atom
If the central atom is positive,
• then subtract 1 electron from the overall electron
total; if the central atom is negative,
• then add 1 electron to the overall electron total.
VSEPR THEORY
4. Add or subtract electrons for charge;
5. Divide the total of these by 2 to find the
total number of electron pairs;
6. Use this number to predict the shape.
CHEMICAL BONDING
MODULE 5B
INSTRUCTOR 1
VALENCE SHELL ELECTRON-PAIR REPULSION
(VSEPR) THEORY, contd
TOTAL ELECTRON BONDING LONE PAIRS EXAMPLES

PAIRS PAIRS
2 2 0 BeCl2
3 3 0 BF3
3 2 1 SO2
4 4 0 CH4
4 3 1 NH3
4 2 2 H2O
5 5 0 PCl5
5 4 1 SF4
5 3 2 ClF3
5 2 3 XeF2
6 6 0 SF6
6 5 1 BrF5
6 4 2 XeF4
INTERMOLECULAR BONDING
MODULE 6
INSTRUCTOR 1
INTERMOLECULAR FORCES OF ATTRACTION
• These are Intermolecular attractions between

one molecule and a neighboring molecule;
• They are forces between permanent dipoles
and exist between all molecules;
• Intermolecular forces affect many physical
properties. For example, viscosity.
• Viscosity, which is the resistance of a liquid to
flow increases with stronger intermolecular
forces.
Types of Intermolecular forces of attractions:
i. Vander Waal’s forces

ii. Dipole-Dipole attractions
VANDER WAAL’S FORCES
• Also known as London Dispersion Forces;

• Weak forces of attraction;
• Cause of temporary dipole movements in the
atoms. It's very notable in the noble gases;
• Van der Waals forces are the weak forces that
contribute to intermolecular bonding between
molecules.
• Van der Waals forces are the sum of the

attractive and repulsive electrical forces
between atoms and molecules.
• These forces differ from covalent and ionic
chemical bonding because they result from
fluctuations in charge density of particles;
• Examples of van der Waals forces include
hydrogen bonding, dispersion forces and
dipole-dipole interactions
Properties of Van der Waals Forces

• They are weaker than either ionic or covalent
chemical bonds.
• They are not directional.
• They act only over a very short range. The
interaction is greater when molecules draw
closer.
• They are independent of temperature, with the
exception of dipole-dipole interactions.
DIPOLE-DIPOLE ATTRACTIONS
These are:
• Instantaneous and induced dipoles
• Dipole-dipole interactions
•
Instantaneous and induced dipoles

• The displacement of electrons causes a normally non-
polar species to become polar. This forms an
instantaneous dipole.
• Following this, electrons in a neighboring atom or
molecule may be displaced, also producing a dipole.
This is a process of induction and the newly formed
dipole is called an INDUCED DIPOLE.
• These 2 events lead to an intermolecular force

of attraction called an instantaneous dipole-
induced dipole attraction or dispersion force or
London force.
• Dispersion forces exist between all the

molecules. Dispersion forces between
molecules are much weaker than the covalent
bonds within molecules.
• The ease with which electron charge density is

distorted by an external electric field i.e. ease
with which a dipole can be induced in an atom
or molecule is called POLARIZABILITY
• Polarizability increases with increased number
of electrons in a specie.
•
DIPOLE-DIPOLE INTERACTIONS
• Permanent dipole-
Exists in all polar molecules due to difference in
E.N values of bonded atoms.
Instantaneous dipole-
• Temporary dipole that exists as a result of
fluctuation in the electron cloud.
Induced dipole-
• Temporary dipole created due to influence of a
neighboring dipole (permanent or instantaneous).
DIPOLE-DIPOLE INTERACTIONS
• In a polar substance, molecules try to line up

with the positive end of one dipole directed
toward the negative ends of neighbor dipoles.
• This additional partical ordering of molecules
causes a substance to persist as a solid or
liquid at temperatures higher than otherwise
expected.
• In low molecular weight alcohols, the

hydrogen-bonding properties of their polar
hydroxyl group dominate other weaker van der
Waals interactions. In higher molecular weight
alcohols, the properties of the nonpolar
hydrocarbon chain(s) dominate and determine
their solubility.
• Example, Ethanol and n-pentane
• Both have equal molecular masses. But due to

significant difference in E.N value between H
and O, there is a large O-H bond dipole
moment in C4H9OH.
• E.N difference between C and H is so small
that the bond dipole moments in C5H12 is
almost zero.
HYDROGEN BONDING
MODULE 7
INSTRUCTOR 1
HYDROGEN BONDING
• Hydrogen bond is a special kind of intermolecular

force of attraction.
• A weak attraction between a lone pair of electrons
on one atom and a covalently bonded hydrogen
atom.
• It is a specific type of strong intermolecular
dipole-dipole interaction between a partially
positively-charged hydrogen atom and a partially
negatively-charged atom that is highly
electronegative, namely N, O, and F
HYDROGEN BONDING
• In hydrogen bonding, an hydrogen atom acts

as a bridge between two non-metal atoms;
• It is much weaker than the ionic or covalent
bonds;
• Hydrogen bonds are examples of van der
Waals forces, a general term for intermolecular
interactions that do not involve covalent
bonds.
HYDROGEN BONDING
• If the hydrogen bonding is intramolecular, i.e.

within the same molecule, involving 1
molecule, there is ring formation or chelation.
(This results into a lower b-pt. than expected).
• If intermolecular (between 2 molecules), it
gives rise to association (produces higher b.pt
than expected).
•
HYDROGEN BONDING
Hydrogen bonds between water molecules:
• Hydrogen bonding in water contributes to its unique
properties, including its high boiling point (100 °C)
and surface tension.
• It is responsible for many of the properties exhibited
by water.
 Hydrogen bonds give water the unique properties that
sustain life. If it were not for hydrogen bonding,
water would be a gas rather than a liquid at room
temperature.
HYDROGEN BONDS
H- BONDING IN WATER
• The hydrogen bonding that occurs in water
leads to some unusual, but very important
properties.
• Most molecular compounds that have a mass
similar to water are gases at room
temperature.
• Water molecules are able to stay condensed in
the liquid state because of the strong hydrogen
bonds.
H- BONDING IN WATER
• H-bonds stabilize the structures of proteins
and DNA, both key ingredients of cells.
• The slightly negative oxygen side of the water

molecule and the slightly positive hydrogen
side of the water molecule are attracted to
each other and form a hydrogen bond.
H- BONDING IN WATER
H- BONDS
H- BONDING IN ACETIC ACID
• In acetic acid, hydrogen bonding leads to the

formation of dimers both in the liquid and
vapor state.
• Hydrogen bonding permits molecules to exist
in stable pairs (dimers) e.g. dimerization of
gaseous acetic acid
DIMERIZATION OF ACETIC ACID
ACETIC ACID DIMERS
INTRA AND INTER H-BOND
• Liquids in which hydrogen bond occurs exhibit
stronger than usual intermolecular forces and
these liquids generally have high heats of
vaporization.
Example:
• O-Nitro-Phenol.
• In O-Nitro-Phenol, chelation is possible. This
hinders Hydrogen bonding with the solvent
H2O molecules. Thus, solubility is lowered.
INTRAMOLECULAR H-BOND
INTERMOLECULAR H-BOND
INTRA AND INTER H-BOND
• o-Nitrophenol forms intramolecular H bond
whereas molecules of p-Nitrophenol get
associated through intermolecular H bond.
The strong intermolecular H bonding increases
the boiling point but intramolecular H bonding
cannot do so.
• Therefore, o-Nitrophenol is more steam
volatile than p-Nitrophenol.
H- BOND AND VISCOSITY
 Hydrogen bonding helps to understand certain

trends in viscosity.
 The hydrogen atoms in alcohols can form
hydrogen bonds with O atoms in neighboring
molecules.
 The more the O-H groups in a molecule, the more
the possibilities for Hydrogen bonding and the
more the resistance to flow and thus the greater
the viscosity of the liquid.
HYBRIDIZATION
OF
ATOMIC ORBITALS
MODULE 8
INSTRUCTOR 1
HYBRIDIZATION OF ATOMIC ORBITALS
• Hybridization is defined as the concept of

mixing two atomic orbitals with the same
energy levels to give a degenerated new type
of orbitals.
• In hybridization schemes, the number of
hybrid orbitals is equal to the total number of
atomic orbitals that are combined
• With hybridization, the shape of the molecule
can be predicted.
HYBRIDIZATION PROCESS
In Hybridization
• Atomic orbitals with equal energies undergo
hybridization.
• The number of hybrid orbitals formed is equal
to the number of atomic orbitals mixing.
• The bigger lobe of the hybrid orbital always
has a positive sign, while the smaller lobe on
the opposite side has a negative sign.
HYBRIDIZATION PROCESS
• During the process of hybridization, the atomic

orbitals of similar energy are mixed together
such as the mixing of two ‘s’ orbitals or two
‘p’ orbital’s or mixing of an ‘s’ orbital with a
‘p’ orbital or ‘s’ orbital with a ‘d’ orbital.
Types of Hybridization
Hybridization can be classified as:

• sp,
• sp2,
• sp3,
• sp3d,
• sp3d2,
• sp3d3.
sp Hybridization
• This type of hybridization involves the mixing

of one ‘s’ orbital and one ‘p’ orbital of equal
energy to give two new equivalent orbitals
known as sp hybridized orbitals.
• It forms linear molecules with an angle of
180°
• Each sp hybridized orbital has an equal
amount of s and p character, i.e., 50% s and p
character.
sp Hybridization
Examples:
• All compounds of beryllium like BeF2,
BeH2, BeCl2
• All compounds of carbon-containing triple
Bond like C2H2.
sp Hybridization
• Electronic configuration of 'Be' in ground state is
1s2 2s2.
• Since there are no unpaired electrons, it
undergoes excitation by promoting one of its 2s
electron into empty 2p orbital.
• Thus in the excited state, the electronic
configuration of Be is 1s2 2s1 2p1.
• In the excited state, the beryllium atom undergoes
'sp' hybridization by mixing a 2s and one 2p
orbitals.
sp Hybridization
• Thus BeCl2 is linear in shape with the bond
angle of 180o.
sp2 Hybridization
• In sp2 hybridization, one s and two p orbitals of

the same shell of an atom mix to form 3
equivalent orbitals called sp2 hybrid orbitals.
• The hybridization is also called trigonal
hybridization.
• A mixture of s and p orbital formed in trigonal
symmetry.
• All the three hybrid orbitals remain in one plane
and make an angle of 120° with one another.
sp2 Hybridization
• Electronic configuration of Boron in ground state is 1s2 2s2

2p1 with only one unpaired electron. Since the formation of
three bonds with chlorine atoms require three unpaired
electrons, there is promotion of one of 2s electron into the
2p sublevel.
• Thus Boron in the excited state has electronic configuration:
1s2 2s2 2px12py1.
• In the excited state, Boron undergoes sp2 hybridization by
using a 2s and two 2p orbitals to give three half filled sp2
hybrid orbitals which are oriented in trigonal planar
symmetry.
• Thus the shape of BCl3 is trigonal planar with bond angles
equal to 120o.
sp2 Hybridization
sp2 Hybridization
• Examples
• All the compounds of Boron i.e. BF3, BH3
• All the compounds of carbon containing a
carbon-carbon double bond, Ethylene (C2H4)
sp3 Hybridization
• When one ‘s’ orbital and 3 ‘p’ orbitals belonging

to the same shell of an atom mix together to form
four new equivalent orbital, the type of
hybridization is called a tetrahedral hybridization
or sp3. The new orbitals formed are
called sp3 hybrid orbitals.
• The angle between the sp3 hybrid orbitals is
109.280
• Each sp3 hybrid orbital has 25% s character and
75% p character.
• Example of sp3 hybridization: methane.
sp3 Hybridization
• The simplest stable hydrocarbon is methane CH4.
• To account for this, an orbital diagram in which
there are 4 unpaired electrons is required.
• Thus, in the excited state, one of the 2s electrons
is promoted to the empty 2p giving four unpaired
electrons;
• The 2s and all the three (3p) orbitals of carbon
hybridize to form four hybrid orbitals called sp3
• The geometry of orbital arrangement due to the
minimum electron repulsion is tetrahedral.
sp3 Hybridization
sp3 Hybridization
sp3d Hybridization
• sp3d hybridization involves the mixing of one s orbital, 3p

orbitals and 1d orbital to form 5 sp3d hybridized orbitals of
equal energy.
• The mixture of s, p and d orbital forms trigonal bipyramidal
symmetry.
• Three hybrid orbitals lie in the horizontal plane inclined at
an angle of 120° to each other known as the equatorial
orbitals.
• The remaining two orbitals lie in the vertical plane at 90
degrees plane of the equatorial orbitals known as axial
orbitals.
• Example: Hybridization in Phosphorus pentachloride (PCl5)
sp3d Hybridization
• The ground state electronic configuration of
phosphorus atom is:
1s2 2s22p6 3s23px13py13pz1.
▪ The formation of PCl5 molecule requires 5

unpaired electrons. Hence the phosphorus
atom undergoes excitation to promote one
electron from 3s orbital to one of empty 3d
orbital.
sp3d Hybridization
• Thus the electronic configuration of 'P' in

the excited state is
1s2 2s22p6 3s13px13py13pz1 3d1.
sp3d2 Hybridization
• Sp3d2 hybridization has 1s, 3p and 2d orbitals,

that undergo intermixing to form 6 identical
sp3d2 hybrid orbitals.
• These 6 orbitals are directed towards the
corners of an octahedron.
• They are inclined at an angle of 90 degrees to
one another.
sp3d2 Hybridization
• The electronic configuration of sulphur in ground
state is 1s2 2s22p6 3s23px23py13pz1.
• In SF6 molecule, there are six bonds formed by
sulfur atom. Hence there must be 6 unpaired
electrons.
• Hence it promotes two electrons into two of the
3d orbitals (one from 3s and one from 3px).
• Thus the electronic configuration of sulphur in
the excited state is 1s2 2s22p6 3s13px13py13pz13d2.
sp3d2 Hybridization
HYBRID ORBITALS AND THEIR
GEOMETRIC ORIENTATION
HYBRID ORIENTATION EXAMPLE PREDICTED
ORBITALS BONDING ANGLE
sp Linear BeCl2 𝟏𝟖𝟎°

sp2 Trigonal planar BF3 𝟏𝟐𝟎°
sp3 Tetrahedral CH4 𝟏𝟎𝟗. 𝟓°
dsp2 Square planar [Ni(CN)4]2 𝟗𝟎°
sp3d2 Trigonal bipyramidal PCl5 𝟏𝟐𝟎°, 𝟗𝟎°
sp3d2 Octahedral SF6 𝟗𝟎°

d2sp3 Octahedral (Co(NH3)6]3+ 𝟗𝟎°
THE NOBLE GASES
GROUP VIII (0), (18)
MODULE 9
INSTRUCTOR 1
NAMES OF THE NOBLE GASES
The noble gases, also known :

➢ the inert gases;
➢rare gases,
➢group VIII
➢group 0 or
➢group 18 (International Union of Pure and
Applied Chemistry (IUPAC) of the periodic
table).
• They were once labeled group 0 in the periodic

table because it was believed they had a
valence of zero, meaning their atoms cannot
combine with those of other elements to form
compounds. However, it was later discovered
that some of them do form compounds;
• Group VIIlA – The electronic structures of the
gases and the finding that some of them do not
indeed form compounds suggest this.
Rare gases/Inert gases :

When discovered and identified, they were
thought to be exceedingly rare as well as
chemically inactive. But it is now known that
several of these elements are quite abundant on
earth and other parts of the universe.
Noble gases:
To reflect the low reactivity of these elements,
ELECTRONIC CONFIGURATIONS
The Electron Configurations for Noble Gases

• Helium 1s2
• Neon [He] 2s2 2p6
• Argon [Ne] 3s2 3p6
• Krypton [Ar] 3d10 4s2 4p6
• Xenon [Kr] 4d10 5s2 5p6
• Radon [Xe] 4f14 5d10 6s2 6p6
PHYSICAL AND ATOMIC PROPERTIES
Elect. Config Atomic

Atomic Atomic Boiling pt Melting 1st Ionization Density
radius
# mass (K) pt (K) (E/kJ mol-1) (g/dm3)
(pm)
1s2
He 2 4.003 4.216 0.95 2372.3 0.1786 31
[He] 2s2 2p6

Ne 10 20.18 27.1 24.7 2080.6 0.9002 38
[Ne] 3s2 3p6

Ar 18 39.948 87.29 83.6 1520.4 1.7818 71
[Ar] 3d10 4s2

Kr 36 83.3 120.85 115.8 1350.7 3.708 88
4p6
[Kr] 4d10 5s2
Xe 54 131.29 166.1 161.7 1170.4 5.851 108
5p6
[Xe] 4f14 5d10
Rn 86 222.1 6s2 6p6 211.5 202.2 1037.1 9.97 120
PHYSICAL AND ATOMIC PROPERTIES
Argon Krypton
Helium Neon Xenon Radon
Enthalpy of vaporization
0.08 1.74 6.52 9.05 12.65 18.1
(kJ/mol)
Solubility in water at 20 °C
8.61 10.5 33.6 59.4 108.1 230
(cm3/kg)
Electronegativity 4.16 4.79 3.24 2.97 2.58 2.60

ABUNDANCE/OCCURRENCE
• All the gases are present in the earth’s atmosphere.

• Most often found as monoatomic gases;
• The abundances in the universe decrease as their
atomic number increase.
• Helium is the most common element in the universe
after hydrogen, with a mass fraction of about 24%;
• Most of the helium in the universe was formed during
big bang nucleosynthesis, but the amount of helium is
steadily increasing due to the fusion of hydrogen and
the alpha decay of heavy elements.
COMMERCIAL SOURCE/ PREPARATION
▪ All from air except He and Rn

▪ Neon, argon, krypton, and xenon are found in air
and are obtained by liquefying it and performing
fractional distillation.
▪ The major source of helium is from the cryogenic
separation of natural gas.
▪ Radon, a radioactive noble gas, is produced from
the radioactive decay of heavier elements,
including radium, thorium, and uranium
GENERAL PROPERTIES
• Noble gases are typically highly unreactive

except when under particular extreme
conditions.
• Exist as colourless, odourless, tasteless, non
flammable gases
• Powerful oxidizing agents
• These elements are gases at ordinary room
temperature and pressure.
GENERAL PROPERTIES
Noble gases are characterized by:

• low reactivity
• low boiling point
• melting and boiling point close to each other
(liquid over a narrow range)
• very low electronegativity
• high ionization energy
• gases under ordinary conditions
REACTIONS
• The larger atoms are easily distorted or

polarized by other charged bodies due to
weaker attraction of the nucleus for the
electrons in the distant valence shell.
• This polarized atom becomes unsymmetrical
though the atom remains electrically neutral.
• Polarizability of the noble gases increases from
He to Rn
COMPOUNDS OF THE NOBLE GASES:
Compounds formation through:

• Coordination
• Excitation
• Induced dipole
• Clathrates formation
COMPOUNDS OF THE NOBLE GASES
Coordination Compounds-
• Very electronegative atoms bond to Kr, Xe, Rn;
• Xenon compounds are the most numerous of the noble gas
compounds that have been formed.
• Most of them have the xenon atom in the oxidation state of
+2, +4, +6, or +8 bonded to highly electronegative atoms
such as fluorine or oxygen;
• Xenon reacts with fluorine to form numerous xenon
fluorides according to the following equations:
• Xe + F2 → XeF2
• Xe + 2F2 → XeF4
• Xe + 3F2 → XeF6
▪ Noble gas fluorides are powerful oxidizing

agents.
• The reactivity follows the order Ne < He < Ar <

Kr < Xe.
CLATHRATES
• They are also known as cage compounds;
• They are compounds of noble gases in which they
are trapped within cavities of crystal lattices of
certain organic and inorganic substances;
• The molecules of the host form a cage-like
crystalline lattice within which there are open
spaces that may be occupied by molecules of a
second compound or element called the guest.
CLATHRATES COMPOUNDS, contd
• No chemical bonds are formed between the two;

• Ar and other heavier ones form clathrates.
• For example, Ar, Kr, and Xe can form clathrates with
crystalline β-quinol, but He and Ne cannot fit because
they are too small.
• He is a small size element with low polarizability.
This makes it a highly mobile gas and it is not trapped
by various structures of other atoms.
USES OF GROUP VIII (O) GASES
• The inertness of the noble gases makes them be to be

useful for many applications;
• They can be used to shield reactive chemicals from
oxygen;
• They are ionized for use in lamps and lasers;
• In the preparation of ultrapure silicon and germanium
crystals and other semiconductor materials used in
transistors’
• The very low boiling points and melting points of the
gases make them useful as refrigerants in the study of
matter at extremely low temperatures;
Helium
• Helium is used in breathing gas mixture by deep-
sea divers to prevent oxygen, nitrogen and carbon
dioxide toxicity.
• He is used in preference to nitrogen to dilute
oxygen in the gas cylinders used by divers.
Due to low solubility of He in fluids, He does
not dissolve in blood. It does not form bubbles
on decomposition as N2 does because nitrogen
is quite soluble in blood
• Helium is used in weather balloon and to fill

airships;
• Helium is used as the flow gas in gas-liquid
chromatography;
• He is used to maintain materials at low
temperatures;
• He has the lowest boiling point of any liquid.
Hence it is used in cryoscopy to obtain very low
temperature for superconductivity and lasers. This
is because helium has the lowest boiling point.
NEON
• Neon is used in neon discharge tubes
ARGON
• The largest use of argon is to provide an inert
atmosphere for metallurgical processes e.g. welding
stainless steel, titanium etc. thus, He and Ar are used to
blanket materials that need to be protected from N2, O2;
• Argon – nitrogen mixture used to fill electric light
bulbs, fluorescent lamps to increase efficiency and life
of the bulbs.
• Argon is used in incandescent lamps to prevent

the hot tungsten filament from oxidizing;
• Smaller amounts of Ar is used in growing
silicon and germanium crystals for transistors;
Xenon has been used as an anesthetic though costly,
it is nonflammable and readily eliminated from the
body.
Radon is highly radioactive. It is only used in
radiotherapy.
THE ALKALI METALS
GROUP 1A
MODULE 10
INSTRUCTOR
1
HISTORY/GENERAL PROPERTIES
• Alkali metals are the chemical elements found

in Group 1 of the periodic table;
• The word "alkali" received its name from the
Arabic word "al qali," meaning "from ashes",
which since these elements react with water to
form hydroxide ions, creating alkaline
solutions (pH>7).
ABUNDANCE/ OCCURRENCE
• Na and K are the 6th and 7th most abundant

elements, making up 2.6% and 2.4% respectively
of the earth’s crust.
• Due to their high reactivities, they are never
found as free metals.
• They are found only in +1 oxidation state and
found combined with other elements in form of
simple or complex compounds. e.g. NaCl, KCl,
KCl. MgCl2. 6H2O (potash magnesium chloride).;
ABUNDANCE/ OCCURRENCE
• Crude phosphate contains 20% of lithium

oxide Li2O.
• Rb and Cs are rare;
• Francium is a natural radioactive isotope and is
very rare. It was just discovered in 1939;
PREPARATION
They are strong reducing agents hence preparation
is by electrolysis of fused salts.
• By electrolytic reduction of fused salt e.g. NaCl

Na+ + e → Na
• The metals can be obtained from their oxides:
• Purification – by distillation.
PROPERTIES OF THE ALKALI METALS—
GROUP 1A
Properties Lithium Sodium Potassium Rubidium Cesium Francium
Atomic no 3 11 19 37 55 87
Elec. config 1s²2sˡ (Ne)(3sˡ) Ar 4s1 Kr 5sˡ Xe 6sˡ Rn 7sˡ

m.pt 179 97.8 63.65 38.89 28.5 -
B.pt 1317 892 753.9 688 671 -
Atomic Radius 1.52 1.85 2.31 2.44 2.62 -
Ionic Radius 0.68 0.97 1.33 1.47 1.67 1.80

Metallic 1.225 1.572 2.025 2.16 2.35 -
Radius
Redox -3.34 -2.271 -2.92 -2.99 -3.02 -
potential
I .E , KJ/mole 519 494 418 406 377 357
Coord .No. 4/6 4/6 6 6 6 -

PHYSICAL PROPERTIES
They have the properties of metals:

• bright silvery metals;
• High ductility and malleability;
• Excellent conductors of electricity and heat;
• Softest metals, softness increases down;
• Low melting point and boiling points. Decreases
down;
• Low ionization energy. Decreases down;
• They are less dense than most elements
CHEMICAL PROPERTIES/REACTIONS OF
ALKALI METALS
• Alkali metals are among the most reactive metals. This

is due in part to their larger atomic radii and low
ionization energies;
• Reactivity increases down the group, from Li to Cs;
• Best reducing agents
• Explosive when exposed to air

• Combine with most non-metals such as halogens,
halogen acids, sulfur and phosphorus to form halides,
sulfides and phosphides;
2𝑀 + 𝑋2 → 2𝑀𝑋
ALKALI METALS
With Halogens,
• They all form simple halides
• Heavier members form polyhalides in addition
e.g. KI3, RbI3 etc.
ALKALI METALS
With H2O
• they all react vigorously and violently, with water,
liberating hydrogen and forming strong caustic
solutions which are highly soluble.
1
Na + H2O → NaOH + H2
2
With Oxygen
▪ Li and Na form monoxides;
• Heavier elements form superoxides. The
peroxides too can be prepared, Li2O2, Na2O2
ALKALI METALS
With hydrogen
• They form ionic hydrides prepared by heating
the metal in dry hydrogen;
2𝑁𝑎 + 𝐻2 → 2𝑁𝑎𝐻
COMPOUNDS OF GROUP 1A METALS
• Most are soluble in H2O and ionic;

• Solutions of compounds are conductive with
Li being the least because Li+ is highly
hydrated hence it’s ion is heavier;
• All Li compounds are hydrated. Many Na
salts are hydrated. Few K salts are hydrated.
No Rb and Cs salts are hydrated.
COMPOUNDS OF GROUP 1A METALS
Hydroxides
• Strong bases. LiOH is least because it is less soluble in H2O;
• Solubility of the hydroxides increases down the group.
Similarly,
• For LiF, NaF, RbF, CsF, µo (lattice energy), decreases from Li to Cs.
Solubility LiF< NaF< RbF< CsF.

COMPLEXES OF ALKALI METALS
• Form few complexes due to large ionic radii

• Because of their low positive charge (+1) and relatively
large ionic radii, alkali metal cations have only a weak
tendency to form metal complexes.
• Complex formation is most significant for the smallest
cation (Li+) and decreases with increasing radius.
• In aqueous solution, for example, Li+ forms the tetrahedral
[Li(H2O)4]+ complex. In contrast, the larger alkali metal
cations form octahedral [M(H2O)6]+ complexes.
ANOMALOUS BEHAVIOUR OF LITHIUM
Lithium and its compounds differ from the other

members of the group.
• It is much harder;
• Has higher melting point;
• Only forms Li2O;
• Readily reacts with nitrogen;
• LiF is insoluble in covalent solvents;
• Li2CO3 and LiF are insoluble in H2O like Mg in
Group 11A but unlike group 1A metals,
ANOMALOUS BEHAVIOUR OF LITHIUM
• LiOH and Mg(OH)2 slightly soluble in

H2O;
• Li salts are heavily hydrated. High
hydration energy of Li+ ion in aqueous
solution due to its small size;
• LiBr and LiI are soluble in many organic
solvents because they have covalent
structures;
USES OF ALKALI METALS
Lithium
• Used in metallurgy as a scavenger of impurities e.g. in
the refining of Fe, Ni, Cu, and Zn;
• Used in the production of certain light metal alloys e.g.
gives high temperature strength to aluminum and
ductility to magnesium;
• Alloyed with Ag for brazing (joining metals together);
• In the manufacture of light weight electrical batteries;
• In the manufacture of H-bombs. Isotope Li gives
tritium gas which when bombarded with neutrons gives
H-bombs
Sodium
• As reducing agent to produce high melting point metals
e.g. Ti, Zr;
• In the detergent industry where sodium alkyl sulfates
are employed;
• NaOH in the manufacture of soap, in petroleum
refining and textiles;
• In the production of dyes and dye intermediates;
• In perfumery;
• As heat transfer fluid in nuclear reactors;
• In the reduction of organic compounds.
Potassium
• Manufacture of fertilizers
• KO2 used in life support systems. A source of
O2 supply in respiratory equipment since it
generates O2 and absorbs CO2.
Rubidium
Minor economic significance;
Cesium
• In nuclear reactors;
• Cesium salts used in photomultiplier tubes, IR
lamps and spectrophotometers
CHEMISTRY OF ALKALINE EARTH
METALS,
GROUP IIA (GROUP 12)
MODULE 11
INSTRUCTOR 1
ABUNDANCE/OCCURRENCE
• the alkaline earth metals are very reactive. Hence they

are never found in elemental form in nature;
• They are found combined with other elements as they
are reactive;
• Be is rare; known as glucinium. Has sweet taste but
poisonous\
• Mg, Ca, Sr, Ba not much;
• Ra is radioactive and occurs in uranium series;
• Magnesium (Mg), calcium (Ca), strontium (Sr), and
barium (Ba) - first isolated in the early 19thcentury.
EXTRACTION/ PREPARATION OF THE ALKALINE
EARTH METALS
• The alkaline earth metals are produced for

industrial use by electrolytic reduction of their
molten chlorides.
CaCl2(l)→Ca +Cl2(g)
• These metal chlorides are obtained from a variety

of sources:
BeO + 2HCl → BeCl2 + H2O
BeO + C + Cl2 → BeCl2 + CO

PREPARATION OF THE ALKALINE EARTH METALS
ii. Chemical reduction

MgO + C → Mg + CO
3BaO + Al → 3Ba + Al2 O3
BaCl2 + 2Na → Ba + 2NaCl
PHYSICAL PROPERTIES
Atomic Ionization
Atomic Mass Oxidation Electron Melting Boiling Redox
Radius Energy
no. (g) State(s) Configuration Point Point potential
(pm) (kJ/mol)
Be 4 9.012 +2 1s22s2 105 899.5 1560K 2742K -1.70
Mg 12 24.31 +1, +2 [Ne]3s2 150 737.7 923K 1363K -2.3
Ca 20 40.08 +2 [Ar]4s2 180 589.8 1115K 1757K -2.87
Sr 38 87.62 +2 [Kr]5s2 200 549.5 1655K 1655K -2.89
Ba 56 137.3 +2 [Xe]6s2 215 502.9 1000K 2170K -2.90
Ra 88 226.0 +2 [Rn]7s2 215 509.3 973K 2010K -2.93

PHYSICAL PROPERTIES
• Harder than alkali metals. Softness increases

from Be to Ra;
• Melting point and boiling points are higher than
group 1 (2 electrons involved in the metallic
bonding);
• Good conductors of heat and electricity;
• Atomic and ionic radii are smaller than alkali
metals;
• Redox potentials are similar to group IA except Be
and Mg are poor reductant
CHEMICAL REACTIONS AND COMPOUNDS
• They are electropositive elements hence the reaction

M + X 2 → MX2
Combustion
• Burns brilliantly in air forming the oxides along with

some nitrides
2Mg + O2 → 2MgO
2Mg + N2 → 2Mg3N2
• Proportion of nitride increases down.

• Film of oxide is formed with the air. Speed of

this reaction increases down. It is protective in
case of Be and Mg but non-protective with
others so that action continues till the metals
have reacted completely. Final product being a
mixture of carbonate with some nitride
• With their low first and second ionization

energies, the group 2 elements almost
exclusively form ionic compounds that contain
M2+ ions.;
• Be, with its higher ionization energy and small
size, forms compounds that are largely
covalent;
• Some compounds of Mg2+ also have significant
covalent character.
Reaction with water

• Be + steam → no action at red heat
• Mg + steam → Mg OH 2 + H2
• Ca + 2H2 O → Ca(OH)2 +H2
With hydrogen to form hydrides

• 𝑀 + 𝐻2 → 𝑀𝐻2
• (Ca, Sr, Ba, Ra at high temperature)
Oxides
All group 2 elements except barium react
directly with oxygen to form the simple oxide
MO.
2𝑀 + 𝑂2 → 2𝑀𝑂
Barium forms barium peroxide (BaO2) because

the larger O22− ion is better able to separate the
large Ba2+ ions in the crystal lattice
• In practice, only BeO is prepared by direct

reaction with oxygen, and this reaction
requires finely divided Be and high
temperatures because Be is relatively inert.
The other alkaline earth oxides are usually
prepared by the thermal decomposition of
carbonate salts:
MCO3(s)−→MO(s)+CO2(g)
They act as reducing agents

• 𝑇𝑖𝐶𝑙4 + 2𝑀𝑔 → 𝑇𝑖 + 2𝑀𝑔𝐶𝑙2
Sulphates
Solubility of Sulphates decreases down the
group.
THERMAL STABILITY OF COMPOUNDS OF GROUP IIA
ELEMENTS
• Increases down just like group I. Be (NO3)2

less stable than Ba (NO3)2
Stability determined by two factors:

• Size of cation;
• Charge on the cation.
SOLUBILITIES OF GROUP II COMPOUNDS
Hydroxides
Solubility of hydroxides increases down the group. Why?
• Ease of ion formation increases
• Lattice energy decreases with increase in size
• Be (OH)2 is covalent because of high polarizing effect of small
size
• Mg OH 2 → Mg ++ + 2OH−
• K sp = Mg ++ OH− = 8.9 × 10−12
Ca OH 2 = 1.3 × 10−6
Sr(OH)2 = 3.2 × 10−4
Ba(OH)2 = 5.0 × 10−3
SOLUBILITIES OF GROUP II COMPOUNDS
• The nitrate salts tend to be soluble, but the

carbonates and sulfates of the heavier alkaline
earth metals are quite insoluble because of the
higher lattice energy due to the doubly charged
cation and anion;
• The solubility of the carbonates and the
sulfates decreases down the group because
hydration energies decrease with increasing
cation size.
OXIDES
• The oxides are ionic, white crystalline solids except

BeO which is partly covalent;
• Melting points are high. Beo 2530°C, MgO 2800°C;
• They are strongly basic except BeO which is
amphoteric;
• All except BeO absorb water vapour (moisture) and
CO2 from the atmosphere forming first the hydroxides,
then the carbonates;
CaO + H2 O → Ca(OH)2 +CO2
• BeO does not react because it is less chemically active
COMPLEXES OF GROUP II METALS
Form complexes due to smaller sizes and the

high charge;
Thus, they have a much greater tendency to form
complexes with Lewis bases than do the alkali
metals
• C-N of 2,4 for Be. Others 6
• C.N of 2- linear geometry;
• C.N of 4 is tetrahedral
• C.N of 6-octahedral
COMPLEXES OF THE ALKALINE EARTH METALS
• Ca and Mg form complexes with EDTA

• BeCl2 – linear in gaseous state but has a
network/chain structure in solid state
• Mg makes use of its 3d shell while Be has no d
shell. Hence Mg can show a coordination
number of 6;
• Thus aqueous solutions of Mg2+ contain the
octahedral [Mg(H2O)6]2+ ion.
USES AND IMPORTANCE OF
GROUP IIA
Be – due to its lightness and wide temperature range, it has many

mechanical uses. It can be used in aircraft production in nozzles
of liquid-fueled spacecrafts and mirrors in meteorological
satellites.
• Production of radiation windows since Be is almost
transparent to x-rays.
• A small percentage of beryllium increases the strength of
copper or nickel alloys, which are used in nonmagnetic,
nonsparking tools (such as wrenches and screwdrivers),
camera springs, and electrical contacts.
GROUP IIA
• The low atomic number of beryllium gives it a very low

tendency to absorb x-rays and makes it suited for applications
involving radioactivity.
• Be and BeO are used in nuclear reactors, and the windows on
all x-ray tubes and sources are made of beryllium foil.
Magnesium
Mg used for structural purposes in car engines, pencil sharpeners
and in many electronic devices such as laptops, cell phones.
• Elemental magnesium is an important component of the
lightweight metal alloys used in aircraft frames and aircraft
and automobile engine parts.
GROUP IIA
• Most commercial aluminum contains about 5% magnesium to
improve its corrosion resistance and mechanical properties;
• Elemental magnesium serves as an inexpensive and powerful
reductant for the production of a number of metals, such as
titanium, zirconium, uranium,:
• TiCl4(l)+2Mg(s)→Ti(s)+2MgCl2(s)
• Magnesium Alloys Are Lightweight and Corrosion Resistant.

Because magnesium is about five times lighter than steel and
50% lighter than aluminum,
GROUP IIA
• Used in fireworks due to its bright white flame

color;
• Mg is vital to body’s health. Chlorophyll the
pigment that absorbs light in plants interacts
heavily with Mg and it is necessary for
photosynthesis;
• MgCO3 (white powder) used by athletes to dry

hands for a firm grip
• Mg(OH)2 or milk of magnesia used as a common
component of laxative
GROUP IIA
Calcium
• Millions of tons of calcium compounds are used every year.
• CaCl2 is used as “road salt” to lower the freezing point of
water on roads in cold temperatures;
• In addition, CaCO3 is a major component of cement;
• An ingredient in many commercial antacids’
• “Quicklime” (CaO), produced by heating CaCO3;
• CaCO3 is used in the steel industry to remove oxide impurities,
• To make many kinds of glass, and also used to neutralize
acidic soil.;
GROUP IIA
Strontium –
• used in alloys
• Used in fireworks. It produces a scarlet flame colour
• SrCl2 to make toothpaste for sensitive teeth;
Barium
• Medical use of BaSO4 in “barium milkshakes” for
identifying digestive problems by x-rays . Thus BaSO4 is
used as a contrast agent for x-ray imaging of the digestive
system
• BaCO3 as rat poison
• Radium – most radioactive. Exposure can cause cancer etc.
SIMILARITIES BETWEEN BE AND AL
• Polarizing power of Be2+ and Al3+ are similar.;

• The ionic radius is small for the higher charge. Their
E.N. values are similar;
• The free metals dissolve in NaOH with evolution of
hydrogen. They are passive towards nitric acid because
they form a protective layer of oxide;
• Their hydrides are amphoteric;
• Their salts are easily hydrolysed;
• Their anhydrous halides (except fluoride) are covalent.
The carbides of both yield CH4 on hydrolysis;
• Hydroxides of Be and Al are amphoteric;
COMPARISON BETWEEN PROPERTIES OF GROUP I
AND II METALS
• Group II have large atoms and hence smaller than group I

• Group II metals are denser and harder than I because of their
sizes and high melting point and boiling point
• Metallic bond in II is stronger than in I. the two electrons in
the outermost shell of group II metals give a greater
electrostatic force
• II metals are divalent while I metals are univalent
• Both are colourless because of inert gas configuration
• Complex formation is rare in both
• Compounds of II are more heavily hydrated e.g. CaCl2.6H2O,
BaCl2.2H2O (Rb, Cs do not form hydrated salts)
• More insoluble salts in group II than in group I.
CHEMISTRY OF HYDROGEN
MODULE 12
INSTRUCTOR 1
ABUNDANCE
• Hydrogen is the most abundant chemical
substance in the universe, especially in stars
and gas giant planets.
• However, monoatomic hydrogen is rare on
Earth because of its tendency to form covalent
bonds with most elements.
• Hydrogen is prevalent on Earth in the form of
chemical compounds such as hydrocarbons
and water.
GENERAL PROPERTIES
• Hydrogen is one of the most important

elements in the world. It is all around us;
• It is a component of water (H2O), fats,
petroleum, table sugar (C6H12O6), ammonia
(NH3), and hydrogen peroxide (H2O2);
• Hydrogen is the smallest chemical element
because it consists of only one proton in its
nucleus;
GENERAL PROPERTIES
• Its symbol is H, and its atomic number is 1;

• At standard temperature and pressure, hydrogen
is a nontoxic, nonmetallic, odorless, tasteless,
colorless, and highly combustible diatomic gas
with the molecular formula H2;
• Hydrogen is the lightest element and will explode
at concentrations ranging from 4-75 percent by
volume in the presence of sunlight, a flame, or a
spark.
PRODUCTION
• The most important industrial method for the

production of hydrogen is the catalytic steam–
hydrocarbon process, in which gaseous or
vaporized hydrocarbons are treated with steam
at high pressure over a nickel catalyst at 650°–
950° to produce carbon oxides and hydrogen:
• CnH2n+2 + nH2O → nCO + (2n + 1)H2
PRODUCTION
• Before 1940 most of the world production of

hydrogen was made by processes based on
coal or coke, the principal one being a water–
gas reaction between steam and red-hot coke:
H2O + C → CO + H2.
• By 1970, relatively little hydrogen was being
produced by such processes.
PRODUCTION
• Small amounts of hydrogen produced by the
electrolysis of aqueous solutions of salt or
sodium hydroxide, the electrode reaction being
H2O + e− → 1/2H2 + OH−.
• The reaction between sulfuric or hydrochloric
acid and an active metal like zinc is utilized to
liberate hydrogen in the laboratory, but such
hydrogen usually contains trace quantities of
volatile hydrides.
LABORATORY PREPARATION OF HYDROGEN
• Hydrogen is prepared in the laboratory by the

action of the dilute hydrochloric acid or dilute
sulphuric acid on granulated zinc;
• Granulated zinc contains an impurity like
copper which acts as a positive catalyst, (A
positive catalyst increases the rate of a
chemical equation). This is the reason why
granulated zinc is preferred over pure zinc for
the laboratory preparation of hydrogen gas.
LABORATORY PREPARATION OF HYDROGEN
• Metal + Dilute acid → Salt + Hydrogen
• Zn + 2HCl → ZnCl2 + H2 ↑
• Zn + H2SO4 → ZnSO4 + H2 ↑
PHYSICAL PROPERTIES OF HYDROGEN
• At standard temperature and pressure,

hydrogen is a nontoxic, nonmetallic, odorless,
tasteless, colorless, and highly combustible
diatomic gas with the molecular formula H2;
• Hydrogen has a density of 0.08988 g/L,
making it less dense than air;
• Hydrogen has a melting point of -259.14 °C
and a boiling point of -252.87 °C;
PHYSICAL PROPERTIES OF HYDROGEN
• The extremely low melting and boiling points

of hydrogen result from weak forces of
attraction between the molecules;
• The existence of these weak intermolecular
forces is confirmed by the fact that, when
hydrogen gas expands from high to low
pressure at room temperature, its temperature
rises, whereas the temperature of most other
gases falls.
ISOTOPES OF HYDROGEN
– Three naturally occurring isotopes of hydrogen

exist:
– protium,
– deuterium, and
– tritium,
– each with different properties due to the difference
in the number of neutrons in the nucleus.
CHEMICAL PROPERTIES OF HYDROGEN
• Despite its stability, hydrogen forms many bonds and is

present in many different compounds.
• Hydrogen gas (H2) burns in air at a very wide

range of concentrations between 4 percent and 75
percent by volume.
• The enthalpy of combustion for hydrogen is -286
kJ/mol;
• 2 H2(g) + O2(g) --> 2 H2O(l) + 572 kJ (286
kJ/mol
REACTIONS & COMPOUNDS
• Atomic hydrogen is very reactive;

• It combines with most elements to form
hydrides (e.g., sodium hydride, NaH);
• It reduces metallic oxides to produce the metal
in its elemental state;
• H2 reacts with oxidizing elements, which in
turn react spontaneously and violently with
chlorine and fluorine to form the
corresponding hydrogen halides.
REACTIONS & COMPOUNDS
• It has two distinct oxidation states, (+1, -1),

which make it able to act as both an oxidizing
and a reducing agent;
• Partial positive charge when reacting with
more electronegative elements such as the
halogens or oxygen and partial negative charge
when reacting with more electropositive
elements such as the alkali metals.
HYDRIDES
• Compounds of hydrogen with less electronegative

elements are known as hydrides;
• Hydrides are classified into three major groups,
depending on what elements the hydrogen bonds
to;
• These are covalent, ionic, and metallic hydrides;
• Hydrogen is absorbed at high temperatures by
many transition metals to form hard, alloy-like
hydrides. These are often called interstitial
hydrides .
HYDRIDES
Examples of Ionic Hydrides:
• NaH, KH, CaH2, etc. These contain hydrogen
as the negatively charged (H–) ion.
HYDRIDES
Covalent Hydrides
• Covalent hydrides are formed when hydrogen reacts
with other similar electronegative elements like Si, C,
etc. The most common examples are CH4 and NH3.
• Generally, compounds that are formed when hydrogen
is reacted with non-metals are called covalent hydrides.
Covalent hydrides are also either liquids or gases.
Example of Covalent Hydrides: SiH4 (silane)
• H2(g)+Cl2(g)→2HCl(g)
• 3H2(g)+N2(g)→2NH3(g)
HYDRIDES
Metallic Hydrides
• Also known as interstitial hydrides;
• It involve hydrogen bonds with transition metals.
• These are usually formed by transition metals and
are mostly non-stoichiometric, hard, high melting
and boiling points.
Examples are:
TiH, cadmium, etc
USES OF HYDRIDES
• They are used as reducing agents in many

chemical industries;
• Hydrides are highly significant in battery
storage technologies such as nickel hydride
batteries;
• They are used as drying agents;
• They are used as strong bases in organic
synthesis;
USES / APPLICATIONS OF HYDROGEN
• In the hydrogenation of carbon monoxide and

organic compounds;
• For example, large amounts of hydrogen are
used in the preparation of methanol by the
reaction
CO + 2H2 → CH3OH
in the presence of certain mixed catalysts
containing zinc oxide and chromium oxide at
high temperatures and pressures
• The largest single use of hydrogen in the world is

in ammonia manufacture, which consumes about
two-thirds of the world’s hydrogen production;
• Ammonia is manufactured by the Haber-Bosch
process, in which hydrogen and nitrogen react in
the presence of a catalyst at pressures around
1,000 atmospheres and temperatures around 500°
c:
N2 + 3H2 → 2NH3.
.
• Another major application of hydrogen is in

the catalytic hydrogenation of organic
compounds. Unsaturated vegetable and animal
oils and fats are hydrogenated to make
margarine and vegetable shortening;
• Hydrogen is used to reduce aldehydes, fatty
acids, and esters to the corresponding alcohols.
• Hydrogen has been used as a primary rocket fuel

for combustion with oxygen or fluorine and is
favoured as a propellant for nuclear-powered
rockets and space vehicles.
• Hydrogen is used in the direct reduction of iron
ores to metallic iron and in the reduction of the
oxides of tungsten and molybdenum to the metals.
• Liquid hydrogen is used in the laboratory to
produce low temperatures.
CHEMICAL BONDING
MODULE 5B
INSTRUCTOR 1
TOTAL ELECTRON BONDING LONE PAIRS EXAMPLES

PAIRS PAIRS
2 2 0 BeCl2
3 3 0 BF3
3 2 1 SO2
4 4 0 CH4
4 3 1 NH3
4 2 2 H2O
5 5 0 PCl5
5 4 1 SF4
5 3 2 ClF3
5 2 3 XeF2
6 6 0 SF6
6 5 1 BrF5
6 4 2 XeF4
CHM102: ALKANES
T.O. Olomola, PhD.

Department of Chemistry,
Obafemi Awolowo University, Ile-Ife
Nigeria.
1
Introduction
Alkanes are aliphatic saturated hydrocarbons that have the general
formula CnH2n+2 i.e. the carbon atoms are surrounded by the highest no of
H-atoms. Pentane for example can be written in the condensed form as
CH3CH2CH2CH2CH3, showing that the C-atoms in pentane are
completely saturated with the maximum number of H-atoms possible.
Alkanes can be unbranched or branched. The C-atoms are sp3 hybridized
and the compounds have a general tetrahedral orientation.
2
Alkanes are found on earth and on other planets. The primary source of
alkanes on earth is petroleum and natural gas. Natural gas consists
mainly of methane with smaller quantities of ethane, propane, butane and
isobutane. Petroleum is a complex mixture of organic compounds formed
from the anaerobic decomposition of plant and animal remains over time,
most of which are alkanes and aromatic compounds. It also contains
small amounts of oxygen-, nitrogen- and sulphur containing compounds.
Refining of petroleum (crude oil) is majorly by fractional distillation to
give gas (C3, C4), gasoline (C5‒C11), kerosene (C9‒C16) and gas oil or
diesel (C15‒C25). Distillation under reduced pressure further gives
lubricating oil and waxes, leaving asphalt behind.
3
It turns out that gasoline obtained straight from distillation of crude
oil is a poor fuel because of the phenomenon of engine knock in
internal combustion engines. The octane number (or rating) of a fuel
is the measure by which its antiknock properties are judged. Straight
chain hydrocarbons are far more prone to induce engine knock than
branched ones. 2,2,4-Trimethylpentane is assigned an octane
number of 100 and heptane is assigned a value of 0. A mixture of
87% 2,2,4-trimethylpentane (isooctane) and 13% heptane would be
rated as 87 - octane gasoline. Catalytic cracking is the method used
to obtain good fuel from high-boiling kerosene fraction (C12-C14).
This method involves the breaking apart of the molecules, which
then rearrange to smaller, highly branched alkanes containing 5‒10
C-atoms. Aromatic compounds also have high octane ratings and are
desirable components of gasoline. Catalytic reforming is the process
by which straight-chain alkanes from straight-run gasoline are
converted into aromatic molecules such as toluene.
4
Important Digression
Organic chemists represent the structural formula of compounds in one
of the following ways:
a. Dash structural formula
It involves drawing the chains of atoms in a straight line and often the
lone pair of electrons are omitted. This shows the connectivity of atoms
in a molecule represented in two dimensions and is a rather convenient
way to draw. It does not represent the actual shape of the molecule
drawn. E.g. H H
H C O C H
H H
b. Condensed structural formula:
Involves writing a formula without showing all the individual bonds. In a
condensed structure, each central atom is shown together with the atoms
that are bonded to it. The atoms bonded to a central atom are often listed
after the central atom (as in CH3CH3 rather than H3C-CH3) even
if that is not their actual bonding order.
5
In many cases, if there are two or more identical groups, parentheses and
a subscript may be used to represent all the identical groups.
When a condensed structural formula is written for a compound
containing double or triple bonds, the multiple bonds are often drawn as
they would be in a Lewis structure. E.g.
 2-propanol can be written as CH3CH(OH)CH3, CH3CHOHCH3,
(CH3)2CHOH.
 2-butene will be written as CH3CH=CHCH3.
c. Bond-Line formula
This is the quickest of all because it only shows the carbon skeleton. In a
line-angle formula (as it is also called), bonds are represented by lines,
and carbon atoms are assumed to be present wherever two lines meet or a
line begins or ends. Nitrogen, oxygen, and halogen atoms are shown, but
hydrogen atoms are not usually drawn unless they are bonded to an atom
that is drawn. The number of H atoms necessary to fulfill the
carbon atom’s valency is assumed to be present.
6
C l
c y c lo b u ta n e
2 - c h lo r o b u ta n e
d. Three Dimensional formula

This type of formula shows the arrangement in space of atoms in a
molecule. In this representation, bonds that project upward out of the
plane of the paper are indicated by a wedge ( ), while those that lie
behind the plane are indicated with a hashed wedge ( ), and those that
lie in the plane of the paper are indicated by a line.
H
H
H H
m e th a n e
7
Nomenclature
1. Choose the longest continuous chain as the parent name.
2
6 4 1
7 5 3
Correct naming – as a substituted heptane.

If two different chains of equal length are present, select the chain with
the larger number of branch points as the parent.
2. Number the chain to give substituents the lowest number (or sum in
cases with more than one substituent).
2 -m e th y lp e n ta n e 3 -e th y l-2 -m e th y lh e x a n e
n o t n o t
4 -m e th y lp e n ta n e 4 -e th y l-5 -m e th y lh e x a n e 8
Unbranched alkanes can be referred to as normal with the designation
n. For example, n-hexane refers to the unbranched hexane –
CH3CH2CH2CH2CH2CH3.
Some common branched alkyl substituents include:
1-m ethylethyl CHCH3
(orisopropyl) CH3
2-m ethylpropyl CH2CHCH3

(orisobutyl) CH3
1-methylpropyl CHCH2CH3
(orsec-butyl) CH3
CH3
1,1-dim ethylethyl C CH3
(ortert-butyl) CH3
Sec stands for secondary, while tert stands for tertiary. They can also
be represented as s and t, respectively.
9
3. Arrange the substituents alphabetically.
4. Name compound ensuring figures are separated by comma, figures
and letters separated by a hyphen. Also use the prefixes di, tri, to show
repetition of substituents. Note that prefixes such as di, tri, sec, tert, etc
do not affect alphabetical order. So dimethyl falls under m and not d in
terms of order. This however does not affect iso or cyclo prefixes (in
such cases i and c are placed accordingly in the name).
4
-
e
t
h
y
l
-
3
,
3-
d
i
m
e
t
h
yl
h
e
x
a
ne
Note: It is important that you are able to give the name of an organic
structure and also that you can draw the correct structure from the name.
Example: Draw the structure of 4-isopropyl-3,4-dimethyloctane
10
Preparation of Alkanes
1. Reduction of alkyl halides: Most alkyl halides react with Zn and
aqueous acid to produce an alkane.
R-X + Zn + HX → R-H + ZnX2
2. From Grignard reagents: Alkyl magnesium halides (RMgX) are

known as Grignard reagents. Grignard reagents react with water or
dilute acids to give alkanes.
CH3CH2MgBr + H2O → CH3CH3 + MgBr(OH)
3. Hydrogenation of alkenes: alkenes may be reduced by passing
their vapours with hydrogen over Raney Ni, Pt or Pd even at room
temperature.
P
t
,
N
i
,
P
d
(
C)
H
+
2
11
4. Wurtz reaction: treatment of an ethereal solution of an alkyl
halide with sodium to leads to the formation of an alkane.
CH3CH2Br + 2Na + BrCH2CH3 → CH3(CH2)2CH3 + 2NaBr
The reaction can be applied to different alkyl halides resulting in
mixed alkanes.
CH3CH2Br + 2Na + BrCH2CH2CH3 → CH3CH2CH2CH3 +
CH3(CH2)4CH3 + CH3(CH2)3CH3
5. From alcohols: Alcohols on heating with concentrated hydroiodic

acid and red phosphorous at 150 °C under pressure in a sealed tube
get reduced to alkanes.

P
/R
H+
H
O
+
I
R
O
H
+
2
H
I 2
2
12
Physical Properties of Alkanes
a. Physical state: At room temperature and pressure, C1-C4
unbranched alkanes are gases, C5-C17 unbranched alkanes are
liquids and unbranched alkanes with 18 or more C atoms are solids.
b. Boiling Point: The boiling points of unbranched alkanes show a

regular increase with increasing molecular weight. Branching of
alkanes however lowers the boiling point. Introduction of other
atoms or functional groups shows increase in boiling point as
polarity increases.
Hexane - 68.7 °C, 2-methylpentane - 60.3 °C, 2,2-dimethylbutane -
49.7 °C
c. Density: As a class, alkanes are the least dense of organic groups.

All alkanes have densities considerably less than 1 g/mL.
This explains why petroleum floats on water.
13
d. Solubility: Alkanes are almost totally insoluble in water because of
their very low polarity and their inability to form hydrogen bonds.
Liquid alkanes and cycloalkanes are soluble in one another, and they
generally dissolve in solvents of low polarity e.g. benzene,
chloroform, carbon tetrachloride.
14
Reactions of Alkanes
Alkanes only have strong sigma (σ) bonds. The fact that the C- and
H-atoms of an alkane have approximately the same electronegativity
results in a roughly equal sharing of the electrons by the bonding
atoms. Thus atoms in alkanes are not partially charged and generally
neither nucleophiles nor electrophiles are attracted to them.
Consequently, alkanes are very unreactive compounds and are
referred to as paraffins (which means “little affinity” for other
compounds). Albeit, they undergo the following reactions.
1. Combustion: complete combustion of alkanes (like other

hydrocarbons) gives water and carbon(IV)oxide and is represented
by the general equation below.
(3𝑛 + 1)
𝐶𝑛 𝐻2𝑛+2 + 𝑂2 → 𝑛𝐶𝑂2 + 𝑛 + 1 𝐻2 𝑂
2
15
2. Pyrolysis: also known as cracking involves heating of alkanes in the
absence of air. Pyrolysis differs from combustion as it happens in the
absence of air and does not involve compound oxidation. The
breakdown of the alkane involves generation of radicals which then
react with each other.
 +C
H
3
C
H
3
+C
H3
16
3. Halogenation: Chlorination and bromination of alkanes may be
brought about by light, heat or catalysts. Iodides are prepared by treating
the chloro- or bromoderivative with sodium iodide in methanol or
acetone.
RH + X2 → No reaction in the dark or at r.t.
ℎ𝑣 𝑜𝑟 ∆
CH4 + Cl2 CH3Cl → CH2Cl2 → CHCl3 → CCl4
This reaction is a radical substitution reaction because radicals are
involved as intermediates and the end result is the substitution of a
halogen atom for one or more of the hydrogen atoms of the alkane. This
reaction gives a mixture of products which can be separated by
fractional distillation. This is a chain reaction with the following stages:
i. Chain initiating step: homolytic cleavage of halogen molecule into
radicals. The energy source for this step is the heat or light supplied.
ℎ𝑣
𝐶𝑙2 𝐶𝑙 . + 𝐶𝑙 .
17
ii. Chain propagating steps: a radical reacts to produce another radical
leading to propagation of radicals. The first propagation step
involving H-atom abstraction is the rate determining step for the
whole reaction.
𝐶𝐻4 + 𝐶𝑙 . → 𝐶𝐻3. + 𝐻𝐶𝑙
𝐶𝐻3. + 𝐶𝑙2 → 𝐶𝐻3 𝐶𝑙 + 𝐶𝑙 .
𝐶𝐻3 𝐶𝑙 + 𝐶𝐻3. → 𝐶2 𝐻6 + 𝐶𝑙 .
iii. Chain terminating steps: combination of any two radicals to form a
molecule brings the reaction to an end by reducing the number of
radicals available for propagation.
𝐶𝑙 . + 𝐶𝑙 . → 𝐶𝑙2
𝐶𝐻3. + 𝐶𝐻3. → 𝐶2 𝐻6
𝐶𝐻3. + 𝐶𝑙 . → 𝐶𝐻3 𝐶𝑙
The radical chlorination of alkanes other than methane follows the
same mechanism described above.
18
However, monochlorination of butane gives two products as shown
in the equation below.
h Cl
C H 3C H 2C H 2C H + C l2 C H 3C H 2C H 2C H 2C l + C H 3C H 2C H C H 3 + HCl
3
b u ta n e 1 -c h lo ro b u ta n e 2 -c h lo ro b u ta n e
28% 72%
Since there are 6 primary protons and 4 secondary protons in butane,

then if the possibility of replacing any proton were the same we
should expect the ratio of the primary to secondary chloride to be
60:40. This suggests that probability alone does not explain the
regioselectivity of the reaction to give the actual yield of products
obtained. The 2-chlorobutane obtained is more than expected thus
suggesting that it must be easier to abstract a hydrogen atom from a
secondary carbon than from a primary carbon. This ease of
abstraction is itself a function of the stability of the radical generated.
19
The stability of radicals is as shown below:
R R R H
RC >RC >HC >HC
R H H H
te
rtia
ry s
eco
nda
ry p
rim
ar
y m
eth
yl
Thus in terms of stability,
C
H
C
H
C
H
3
2C
H
3>
C
H
C
3H
C
H
C
H
2
32
A secondary alkyl radical obtained by abstraction of H-atom from an
internal carbon of butane by a chlorine radical is more stable than the
primary radical formed by a hydrogen atom abstraction from a terminal
carbon. It has been experimentally determine that it is 5.0 times easier
for chlorine radical to abstract a hydrogen atom from a tertiary carbon
than from a primary carbon, and it is 3.8 times easier to abstract a
hydrogen atom from a secondary carbon than from a primary carbon.
Thus, relative rates for alkyl radical formation from chlorine radical for
primary, secondary and tertiary protons is 1.0, 3.8 and 5.0,
respectively.
20
Relative amount of product = probability (number of protons) ×
reactivity
Relative amount of 1-chlorobutane = 6 × 1.0 = 6.0

Relative amount of 2-chlorobutane = 4 × 3.8 = 15.2
Sum of the relative amounts of all the alkyl halide products

= 6.0 + 15.2 = 21.2
6
Yield of 1-chlorobutane = × 100% = 28.3%
21.2
15.2
Yield of 2-chlorobutane = 21.2
× 100% = 71.7%
21
Conformation of alkanes
The temporary molecular shapes that result from rotation of groups
about single σ-bonds are called conformations of a molecule. Each
possible structure is called a conformer. An analysis of the energies
associated with a molecule undergoing rotation about a single bond
is called conformational analysis. In conformational analysis, the
Newman projection is used. In a Newman projection, an observer’s
focus in on the conformation around a particular C‒C bond by
sighting down the bond to see the arrangement of the atoms on the
carbons relative to each other. The three lines emanating from the
center of the circle represent the bonds coming from the front
carbon, with respect to the observer. The big circle in the back
represents the back carbon, and the three lines coming off the big
circle represent the bonds coming off the back carbon.
22
The two unique conformations in ethane are staggered and eclipsed,
with the staggered conformation being 11.8 kJ/mol lower than the
eclipsed and consequently the more favoured conformation.
Saw horse and Newman Projections
Energy diagram for rotation in ethane. Only two of the hydrogens are shown for
23
clarity. For ethane, the rotational energy barrier is 2.9 kcal/mol.
The figure above illustrates the change in distance between the C‒H
bonds in the staggered and eclipsed conformations of ethane. A
staggered conformation of ethane is more stable than an eclipsed
conformation because the staggered conformation maximizes the
separation of the electron pairs in the molecular orbitals of the C‒H
bonds. In the eclipsed conformation, the hydrogens are closer; thus,
the repulsions of the electron pairs are greater. The increase of
energy associated with eclipsed bonds on adjacent atoms torsional
strain.
24
Now consider about the C2‒C3 bond in butane, we find that there are 6
important conformations. The structure of butane has two distinctly
different staggered conformations. In one, the two methyl groups have
a gauche conformation. In the other, the two methyl groups have an anti
conformation. In the gauche conformation, the torsional angle between
the two methyl groups is 60°. For the anti conformation, the two methyl
groups have a torsional angle of 180°. The anti and gauche
conformations of butane have an energy difference of 0.8 kcal/mole.
The anti conformation is more stable than the gauche conformation
because the two methyl groups are farther apart in the anti
conformation. Thus, the anti conformation has less van der Waals strain
than the gauche conformation. The van der Waals radius of a hydrogen
atom is 120 pm, and that of a methyl group is 200 pm - nearly twice as
large as a hydrogen. Because the methyl groups of butane are closer in
the gauche conformation than they are in the anti, the compound has
greater van der Waals strain in the gauche conformation.
25
At 25 °C, about three times as many butane molecules have the anti
conformation as the gauche conformation. The other 2 eclipsed
conformations correspond with an energy level of 14 and 24 kJ/mol
relatively higher than the minimum energy of the anti-conformation.
Steric strain (also known as Van der Waal’s strain) is the strain in a
molecule caused when two atoms or groups of atoms are forced closer
together than their atomic radii allow. Every atom or group of atoms
has a measure of size called its van der Waals radius. When two groups
that are not bonded to each other get within close distance of their van
der Waals radii, they begin repelling one another. The electrons
surrounding one group repel the electrons surrounding the other group.
The van der Waals radii indicate how close two groups can approach
each other before these electron-electron repulsions occur. Chemists
call such repulsion van der Waals strain.
C
H3
H
3C H
H H 26
H
Butane has two distinct eclipsed conformations about its C2‒C3 bond.
In one, the two methyl groups eclipse each other. In the second, each
methyl group eclipses with a hydrogen atom. Both conformations have
the same number of eclipsed bonds and the same amount of torsional
strain. However, the methyl‒methyl eclipsed conformation has
significantly more van der Waals strain than does the methyl‒hydrogen
eclipsed conformation. The greater strain arises from the larger methyl
groups that take up more space, and thus have more electron repulsion,
than the hydrogens.
Energy diagram for rotation about the C2‒C3 in butane 27

End of Lecture 1
28
CHM102: ALKENES
T.O. Olomola, PhD.

Nigeria.
1
Introduction
Alkenes (sometimes referred to as olefins) are unsaturated hydrocarbons
in which there is at least one C‒C double bond in which each C-atom
makes use of three sp2 hybrid orbitals to form three σ bonds and both
central C-atoms use the remaining p-orbitals to form a pi bond. Acyclic
(non-cyclic) alkenes have the general formula CnH2n. The double bond is
the functional group in alkenes and is made up of a sigma and a pi bond.
The π-bond is weaker than a σ-bond. The sp2 orbital has more s character
when compared to the sp3 analogue in alkanes, hence due to the
proximity of the s orbital to the nucleus, the effective size of the sp2
orbital decreases in comparison to an sp3. Thus an sp2-s carbon-hydrogen
bond is shorter than an sp3-s carbon-hydrogen bond. The C=C bond in
ethane (1.33 Å) is shorter than the C-C bond (1.54 Å) in ethane.
Ethene is used in the ripening of foods, and in preparation of solvents
like ethylene dichloride, glycol etc. Ethene and propene are very useful
in the polymer industry in the manufacture of polyethylene,
polypropylene, polyvinylchloride, teflon etc.
2
Alkenes are also very useful in the drug and pesticide industries.
Nomenclature
Common names are still used for referring to many simple alkenes.
B
r
C
l
e
thy
le
ne p
ro
pyle
ne v
in
ylc
hlo
rid
e a
lly
lbr
omid
e
1. The IUPAC naming is the most common way of naming alkenes. The
parent compound is the longest continuous chain containing the C=C.
Simply replace the ending -ane of alkane with -ene. E.g.
3
-
p
r
o
p
y
l
-
1
-
h
e
pt
e
n
e
2. Number the parent compound from the end nearest the C=C. If even,
number to give lowest sum for substituent position.
2-methyl-4-octene
3
3. Use an appropriate prefix to indicate the stereochemistry of the alkene.
The lack of easy rotation about double bond gives rise to configurational
or geometrical isomers denoted by cis (same side) or trans (across). Cis
and trans can be used to assign the geometric isomerism in simple
disubstituted alkenes e.g.
c
i
s
-2
-b
u
t
e
ne t
r
a
ns
-2
-
b
ut
e
ne
If two similar groups bonded to the carbons of the double bond are on
the same side of the bond, the alkene is the cis isomer. If the similar
groups are on opposite sides of the bond, the alkene is trans.
Note: For an alkene to have geometrical isomers, the groups attached to

both C-atoms bearing the double bond have to be different. Geometrical
isomers are diastereomers. There is no isomer of propene for instance
(CH2=CHCH3).
4
Stability of Alkenes
Studies of numerous alkenes reveal that the greater the number of
attached alkyl groups to the double bond, the greater the stability of
the alkene. The stabilities of different alkenes as they hydrogenate to
give alkanes is determined by comparing the heats of
hydrogenation. The order is:
RRRR
R HRHRRRHHH
> >
> > > >
RRRH
R HHRHHHHHH
Question:
5
Preparation of Alkenes
1. Dehydrohalogenation of alkyl halides
Dehydrohalogenation is the removal of a hydrogen and a halogen
from an alkyl halide to form an alkene. This involves an elimination
reaction using hot alcoholic base such as ethanolic KOH or KOEt.
Details of elimination reactions would be discussed later.
H
C
l
H E t
O
H
H
C
C
CHK
O
HC
+ H
C
H
=
C
3H
2

H
H
H
In some cases, only a single product is possible, however
dehydrohalogenation of many alkyl halides yields more than one
product. For example, 2-bromo-2-methylbutane will yield two
products: 2-methyl-2-butene and 2-methyl-1-butene. Using a small
base such as ethoxide or hydroxide ion gives the major product as
the more stable alkene.
C
H
3KO
H/
E
tH C
O H
3 CH
2
H
C
H
3C
2C
CH
3 HC
3H
C C +
HC
3H
2C
C
70
°
C CH
B
r CH
3 3
2
-
m
et
h
yl
-
2-
bu
t
e
ne2-
m
et
h
yl
-
1-
bu
t
e
ne6
69
% 31
%
The transition state leading to the formation of 2-methyl-2-butene is
more stable than that of 2-methyl-1-butene (i.e. involves a lower
free energy of activation), and therefore the rate of its formation is
faster (kinetic control).
2. Dehydration of Alcohols
Heating most alcohols with a strong acid causes them to lose a
molecule of water and form an alkene. This is also an elimination
reaction and is favoured at high temperatures. Bronsted acids such
as sulphuric acid and phosphoric acid are often used in the
laboratory. Alumina could also be used at high temperatures.
H
SO C
C
H
3C
H
2H 24 H
O 2C
H
2
1
6
0
17
0°
C
M
e
c
ha
ni
s
m:
H OH
2-
HO -
H
2
C
HC
H
32O
H C
H
3C
H
2 C
HC
H
32 H
C
2CH
2
HO
H
H
CCH
HH 7
3. Dehalogenation of vicinal dihalides
Vicinal dibromides (alkyl halides with two bromines on adjacent
carbon atoms) are converted to alkenes by reduction with either iodide
ion in acetone or zinc in acetic acid.
N
aI
B
r a
ceto
ne
CC CC +I
B r+N
aB
r
Br
B
r C HCO
O
H
3
+ Z
nB
r
2
CC +
ZnC C
Br
4. Partial reduction of alkynes

Controlled reduction of alkynes with hydrogen using palladium
catalyst. Pd
H
C
C
H
H
+
H
C
C
H
2
2
2
8
Some alkynes can be reduced to give cis or trans alkene depending on
the catalyst used. H C
3 CH 3
d
n
ia
la
c
r.
t C
Cc
is
L
/
H
2
H
H
H
C
C
3CC
H
3
N
a
/
Li
q
.N
H
CH 3
H C
3 HC
C
Ht
r
an
s
3
Preparation of
Alkenes
9
Physical Properties of Alkenes
Alkenes just like other hydrocarbons are non polar organic
compounds. Alkenes with two to four carbon atoms are gases, those
with five to seventeen carbon atoms are liquids, while those with
eighteen plus carbon atoms are solids at room temperature and they
burn in air with luminous smoky flame. Alkenes are insoluble in
water but soluble in non-polar solvents. They are also less dense
than water. Alkenes have a lower boiling point than their
corresponding alkanes.
10
Reactions of Alkenes
1. Addition Reaction
The π-bond is particularly susceptible to electron-seeking reagents, i.e.
electrophiles such as positively charged ions and Lewis acids. Thus
alkenes are said to undergo electrophilic addition.
A. Symmetrical reagents:
i. Reduction with H2: Alkenes can be readily hydrogenated under
pressure in the presence of a catalyst. Raney nickel is effective at
room temperature and atmospheric pressure. Both hydrogen atoms
usually add from the same side of the molecule, this is called a syn
addition (same side or face addition).
Pt, Ni, Pd(C)
+ H2
11
The opposite of syn addition is an anti addition and an illustration of
both forms of addition is shown below.
on
C C
i t i Y
n add X
S y
C C + X Y
A n
ti a Y
dd
itio C C
n
X
ii. Halogenation: Alkenes react rapidly with chlorine and bromine in

non-nucleophilic solvents to form vicinal dihalides. When bromine is
used for this reaction, it can serve as a test of unsaturation with the
visual disappearance of the reddish-brown colour of bromine.
Mechanistically, as the bromine molecule approaches an alkene, the
electron density of the alkene π bond repels electron density in the
closer bromine atom, polarising the bromine molecule and making the
closer bromine atom electrophilic.
12
The alkene donates a pair of electrons to the closer bromine, causing
displacement of the distant bromine atom. As this occurs, the newly
bonded bromine atom, due to its size and polarizability, donates an
electron pair to the carbon that would otherwise have been a
carbocation, thereby stabilizing the positive charge by delocalization.
The free bromide ion then attacks at the back side of the other carbon
atom in a substitution reaction, causing the ring to open and resulting
in the formation of a vicinal dibromide.
B
r
-
+B
r
B
r B
r
B
r
B
r
The addition of bromine follows an anti addition, hence the reaction
products are trans.
-
5
°C B
r
+B
r
2
C
Cl
4 B
r
13
B. Unsymmetrical reagents:
i. Hydrohalogenation: These reactions are carried out by dissolving
the hydrogen halide in a solvent such as acetic acid or DCM, or by
bubbling the gaseous HX directly into the alkene, allowing the alkene
to serve as solvent. Order of reactivity of hydrogen halides is HI>
HBr> HCl> HF, and unless the alkene is highly substituted, HCl
reacts so slowly that the reaction is not one that is useful as a
preparative method.
Addition of HX to an unsymmetrical alkene yields one major product
and this can be easily predicted using the rule formulated by Russian
Chemist Vladimir Markovnikov in 1870. The rule simply states that
in the ionic addition of an unsymmetrical reagent to a double bond,
the positive portion of the adding reagent attaches itself to a carbon
atom of the double bond so as to yield the more stable carbocation as
an intermediate.
14
-
+HB
r +B
r
B
r
n
ot
+H
Br
B
r
Carbocations (just like radicals) are intermediates that are classified
according to the number of alkyl substituents that are bonded to the
positively charged carbon. More alkyl groups bonded to a positively
charged carbon decreases the concentration of the positive charge
thereby increasing the stability of the carbocation. Tertiary
carbocations are more stable than secondary and the secondary
carbocations are more stable than primary.
RRHH
R
C
> >
H
>
R
CC
R
C
RHHH
t
e
r
t
i
a
r
ys
e
c
o
n
d
a
r
ym
p
r
i
m
a
r
ye
t
h
y
l
c
a
r
b
o
c
a
t
i
o
nc
a
r
b
o
c
a
t
io
n
c
a
r
b
o
c
a
t
i
o
n 15
When a reaction that can potentially yield two or more constitutional
isomers actually produces only one (or majorly one), the reaction is said
to be regioselective. Addition of HX to unsymmetrical alkenes is
regioselective.
The addition of HI to 2-methyl-2-butene gives 2-iodo-2-methylbutane

as the predominant product with only a small amount of 2-iodo-3-
methylbutane. The more stable tertiary carbocation is formed more
rapidly than the less stable secondary carbocation, so the major product
of each reaction is the one that results from forming the tertiary
carbocation.
H
I
+ +
I I
2
-
m
e
t
h
y
l
-
2
-
b
u
t
e
n
e 2
-
i
o
d
o
-
2
-
m
e
t
h
y
lb
u
t
a
n
e
2
-
i
od
o
-
3
-
m
e
t
h
y
l
b
ut
a
n
e
m
a
j
o
r
p
r
o
d
uc
tm
i
n
o
r
p
r
o
d
u
c
t
16
There is an exception to the Markovnikov’s rule, which occurs when
HBr is added to alkenes in the presence of peroxides (ROOR). When
alkenes are treated with HBr in the presence of peroxides, an anti-
Markovnikov addition occurs.
R
O
O
R
+
H
B
rC
H
C
HC
H
B
r
32
2
HF, HCl and HI do not give anti-Markovnikov addition even when
peroxides are present.
ii. Hydration: Addition of water to an alkene results in no reaction as
water itself is too weakly acidic to afford sufficient hydrogen
electrophile required for the reaction. However in the presence of an
acid, the reaction takes place resulting in the formation of an alcohol.
This acid catalyzed hydration (addition of water) of an alkene, often
used industrially, follows the Markovnikov’s rule and is regioselective.
17
Since acid-catalysed hydration also involves the generation of
carbocations, rearrangements leading to more stable carbocation species
take place. Strong acids such as sulphuric, hydrochloric or phosphoric
acid are often used to catalyse this reaction.
slow fast
H OH2 CH3CHCH3 + H2O CH3CHCH3
H3CHC CH2 +
OH
H
H2 O
fast
CH3CHCH3 + H3O+
OH
iii. Halohydrin formation: If bromination or chlorination of an alkene is

carried out in aqueous solution, haloalcohols called halohydrins (HO-X+)
are formed. The first step of the reaction is similar to the regular halogen
addition but in the second step water rather than the halide ion is the
nucleophile that attacks and opens the halonium ring. The reaction
follows a Markovnikov addition. 18
Cl2/H2O
H3CHC CH2 H3CHC CH2Cl
- +
(HO Cl ) OH
H
H 2O O H H2O
OH
+ Br-
Br Br Br
Br
Br
CH3
CH3 Br2/H2O
OH
Br
Organic molecules are only sparingly soluble in water as solvent.
Thus this reaction is preferrably done in a miture of organic solvent
and water using N-bromosuccinimide (NBS) as electrophilic bromine
source.
O O
H O
B
r
D
MSO
,H
2O
NB
r + N
H
+
O O
19
Note: The aromatic group does not react
2. Oxidation
Alkenes undergo a number of reactions in which the C‒C double bond
is oxidized and some of these lead to cleavage of the double bond
altogether.
A. Syn Dihydroxylation:
The addition of hydroxyl groups to an alkene double bond leading to
the formation of a glycol (1,2-diol) is called hydroxylation. This
reaction takes place using either osmium tetroxide or potassium
permanganate and in both cases a syn addition takes place involving
cyclic intermediates. Osmium tetroxide is more widely applied, though
it is highly toxic, volatile and expensive. Osmium tetroxide reacts with
alkenes in a concerted step to form a cyclic osmate ester. Hydrogen
peroxide hydrolyzes the osmate ester and reoxidizes osmium to
osmium tetroxide. Aqueous sodium sulphite or aqueous sodium
hydrogensulphite can also be used to hydrolyse the osmate ester to give
the glycol. pyridine H2O2
+ OsO4
C C C C
O O HO OH
Os
O O
Os O O
20
O O osmate ester
Methods have been developed for catalytic use of OsO4 in conjunction
with a co-oxidant such as N-methylmorpholine N-oxide (NMO).
A cold, alkaline solution of potassium permanganate adds to the alkene

double bond to form a cyclic manganate ester, which is hydrolysed in
basic solution giving a glycol and a brown precipitate of manganese
dioxide. This permanganate oxidation of alkenes provides a simple
chemical test for the alkene (or alkyne) functional group (Baeyer’s
test). When an alkene is added to a clear, deep purple aqueous solution
of potassium permanganate, the solution loses its purple colour.
+M
n
O HH O
H +M
n
O2
4 HH
O
O H
O
2
H
OO
H
Mn
OO
21
B. Epoxidation of Alkenes:
An epoxide is a three-membered cyclic ether, also called an oxirane.
The most widely used method for synthesis of epoxides is the reaction
of an alkene with a peroxy acid (or peracid). A commonly used peroxy
acid is meta-chloroperoxybenzoic acid (m-CPBA).
OO O
+
R
C
H
C
H R
C
H
C+
HR
C
O
H
2R
C
O
O
H 2
Epoxidation of an alkene is a concerted reaction and it is stereospecific.

The oxygen adds from one phase of the double bond as shown in the
mechanism for the reaction illustrated below. Thus a cis alkene gives
rise to a cis epoxide and a trans alkene gives rise to a trans epoxide.
m
-
C
PB
A O
t
r
a
ns
-
st
i
l
l
be
ne t
r
a
ns
-
st
i
l
l
be
ne
o
x
i
de
22
More substituted alkenes epoxidizes faster and thus when 1,2-
dimethylcyclohexa-1,4-diene is treated with m-CPBA, the more
substituted alkene gets epoxidized.
m
-
C
P
B
A
O
Direct anti hydroxylation of an alkene is possible by using an acidic

aqueous solution of a peroxyacid such as peroxyacetic acid and
peroxyformic acid. Under these conditions, the epoxide is hydrolyzed
to the glycol once it is formed.
O
H
C
C
O
O
H
3
+
H
,
H
O
2
H
O
O
H
23
C. Oxidative Cleavage of Alkenes:
i. Ozonolysis: When an alkene is treated with ozone at low temperatures,
the double bond breaks to give ketones and aldehydes. When ozone is
added to an alkene, a concerted cycloaddition reaction (the oxygen atoms
add to the two carbons in a single step) takes place leading to the
formation of an unstable molozonide which rearranges to an ozonide
intermediate. The ozonide on treatment with a reducing agent such as
zinc metal in acetic acid or dimethyl sulphide, is converted into carbonyl
compounds.
If the ozonide is cleaved by an oxidizing agent such as hydrogen
peroxide the products will be ketones and/or carboxylic acids (the
aldehyde initially gets oxidized to a carboxylic acid).
reductive workup
Zn/HOAc R R
C O + O C
or (CH3)2S R H
R R R O R
R R R C C H
C C R H
R H O O O O
O O O R R
O H2O2 C O + O C
molozonide ozonide R
oxidative workup OH 24
A typical example of an oxidative cleavage is given below.
1
.
O
3
,-
7
8°
C O
+O
2
.
Z
n/
H
OA
c
2
-
m
e
t
h
yl
-
2
-
he
x
e
n
e b
u
t
a
na
la
c
e
t
o
ne
ii. Permanganate Cleavage: If a basic solution of potassium

permanganate used to treat an alkene is warm, too concentrated or if
the solution is acidic, the reaction will not stop at the diol, rather
oxidative cleavage takes place. If the reaction is carried out under basic
conditions, any carboxylic acid product will be in its basic form if the
reaction is carried out under acidic conditions, any carboxylic acid
product will be in its acidic form. A terminal alkene group is oxidized
to carbon dioxide and water.
+ K
Mn
O
O K
Mn
O,H
4 ,O
4 H O
+O +
O
H  O
O
25
End of Lecture 2
26
CHM102: ALKYNES
T.O. Olomola, PhD.

Nigeria.
1
Introduction
Alkynes (also called acetylenes) are unsaturated hydrocarbons that
contain a carbon-carbon triple bond. Acyclic alkynes have the general
formula CnH2n-2. Due to their sp hybridization, they have a bond angle of
180° and so are linear. Although alkynes are not as widespread in nature
as alkenes, the chemical properties of alkynes are similar to those of
alkenes. The only difference is that there are twice as many π bonds to
react. The triple bond is made of two π bonds and one sp-sp σ bond.
There are two classes of alkynes ‒ monosubstituted (terminal) and
disubstituted (internal).
Ethyne (acetylene) is used in oxyacetylene flame for welding and cutting

metals. It is also used as a starting material for manufacture of
acetaldehyde, acetone and benzene for industrial use. Ethyne is used as a
starting material for the manufacture of PVC, polyvinyl acetate and
synthetic rubber.
2
Nomenclature
Alkynes follow the general rule of hydrocarbon nomenclature. The suffix
-yne is substituted for `-ane' in the base hydrocarbon name to denote
alkyne and the position of the triple bond is indicated by its number in
the chain. Numbering begins from the chain end which is nearer the
triple bond. If the triple bond is at the end of the chain, the alkyne is
classified as a terminal alkyne. Alkynes with triple bonds located
elsewhere along the chain are called internal alkynes. For example, 1-
butyne is a terminal alkyne and 2-pentyne is an internal alkyne.
1
-
b
ut
yn
e 2
-
p
en
ty
n
e
Alkynes can also be named as substituted acetylene. Using this common
nomenclature, 1-butyne is named as ethylacetylene and 2-pentyne as
ethylmethylacetylene.
3
Preparation of Alkynes
1. From Calcium carbide: Acetylene can be prepared by the action
of water on calcium carbide, which itself is prepared by the reaction
between calcium oxide (from limestone) and coke (from coal) at the
very high temperatures of the electric furnace.
C aC2 + 2 H 2O H C C H + Ca( OH )
2
2. Dehydrohalogenation of alkyl dihalides: is particularly useful
since the dihalides themselves are readily obtained from the
corresponding alkenes by addition of halogen. This amounts to
conversion by several steps of a double bond into a triple bond.
Br
B r2 K O H , E tO H N aN H 2
 Br
Br
Under mild conditions, dehydrohalogenation stops at the vinyl
halide stage; more vigorous conditions using a stronger base is
required for alkyne formation.
4
3. Reaction of sodium acetylides with primary alkyl halides:
The negative charge and unshared electron pair on carbon makes the
acetylide anion strongly nucleophilic. As a result, an acetylide anion
can react with an alkyl halide substituting the halogen group.
H H
H
CN
a+
C H
CC
l H
C
CC
H+N
a
Cl
H H
This is a method of building higher alkynes from terminal ones.

N
aN
H
2 H
C
CC
CH
C
HC
HC
H
C
H
C
3CH H
C
3C
CN
a+
CC
H
H
3C
H
2C
H
2B
r
2 3 2223
5
Physical Properties of Alkynes
Alkynes have physical properties similar to those of alkanes and
alkenes in general. They are insoluble in water but soluble in
organic solvents with low polarity such as benzene and ether. They
are less dense than water and, like other homologous series, have
boiling points that increase with increasing molecular weight.
Internal alkynes have higher boiling points than terminal alkynes.
Substituted alkynes have small dipole moments due to differences in
electronegativity between the triple-bonded carbon atoms, which are
sp hybridized, and the single-bonded carbon atoms, which are sp3
hybridized.
6
Reactions of Alkynes
1. Addition reaction: Addition of hydrogen, halogens, and hydrogen
halides to alkynes is similar to addition to alkenes, except that here two
moles of reagent is required per triple bond. it is however possible, by
proper selection of conditions, to limit reaction to the first stage of
addition, formation of alkenes. YZ
YZ CC
CC + YZ CC
YZ YZ
2. Reduction to Alkenes: Controlled reduction of alkynes to alkenes is
possible. Predominantly trans-alkene is obtained by reduction of alkynes
with sodium or lithium in liquid ammonia. Almost entirely cis-alkene is
obtained by hydrogenation of alkynes with several different catalysts
such as Lindlar's catalyst. Na, liq. NH 3 H C 2H 5
C 2H 5 H
C 2 H 5 C CC 2 H 5
C 2H 5 C 2H 5
H H 7
H 2 , Lindlar cat.
3. Reactions of acidic hydrogen: Terminal alkynes are weakly acidic.
The average distance of a 2s electron from the nucleus is less than the
average distance of a 2p electron from the nucleus. Therefore, the
electrons in an sp hybrid orbital (50% s character) are closer, on
average, to the nucleus than those in an sp2 hybrid orbital (33.3% s
character). The sp hybridized carbon is more electronegative. Hence
an alkyne attracts the electrons towards itself and therefore a terminal
H can be readily removed as H+ resulting in an acetylide ion.
Addition of terminal alkyne to sodamide dissolved in ether yields
ammonia and sodium acetylide.
H
C
C
C
H
3+
N
a
NH
2H
3N
a
C
C
C
+N
H
3
Terminal alkynes react with certain heavy metal ions, mainly Ag+ and
Cu+, to form insoluble acetylides. When a terminal alkyne is passed
into ammoniacal silver nitrate solution, silver acetylide (white) is
precipitated. This reaction can be used to differentiate
terminal alkynes from non-terminal alkynes.
8
4. Hydration of alkynes: Passage of alkynes into dilute sulphuric
acid in presence of mercuric sulphate as catalyst results in the
addition of one molecule of water to the alkyne leading to the
formation of either an aldehyde or a ketone.
H 2S O 4
+ H 2O R C CH2 R C CH3
R C CH
H gSO 4 OH O
enol k e to n e
9
A structure with OH attached to double bond carbon is called an enol
(ene for alkene, -ol for alcohol). The vinyl alcohol (enol) expected as
product for this reaction is not obtained, rather the enol intermediate
is transformed into the keto. There is an equilibrium between the two
keto and enol structures, this equilibrium is called tautomerism. The
equilibrium generally lies very much in favour of the keto form.
Compounds whose structures differ markedly in arrangement of
atoms, but which exist in equilibrium, are called tautomers.
5. Oxidation cleavage of alkynes: Alkynes react with ozone or basic

potassium permanganate to form carboxylic acids.
1. KM nO 4, OH 1. O3
HCOOH+ RCOOH RCCH HCOOH+ RCOOH
2. H + 2. HOAc
3O
10
Concept of double bond equivalence
The Double Bond Equivalence (DBE) is the number of pairs of hydrogen
atoms that must be subtracted from the molecular formula of the
corresponding alkane to give the molecular formula of the compound.
a. Consider cyclohexane with the formula C6H12

Formula of corresponding alkane is C6H14
Difference is H2 i.e. 1 pair of hydrogen atoms
DBE = 1
b. Consider cycohexa-1,4-diene with the formula C6H8

Formula of corresponding alkane is C6H14
Difference is 3H2 i.e. 3 pairs of hydrogen atoms
DBE = 3
In general, for a compound with the fomula CaHbOcNd,
2𝑎 + 2 − (𝑏 − 𝑑)
𝐷𝐵𝐸 =
2 11
Note:
A DBE of 1 can represent 1 ring or 1 double bond.
A DBE of 2 can be 2 rings or 1 ring and 1 double bond or 2 double
bonds or 1 triple bond.
The importance of DBE is clearly seen when the formula of a compound
is provided and there is need to deduce the structure from such. The DBE
helps one make an intelligent guess of what the possible structure of the
compound would be.
12
End of Lecture 3
13
CHM102: ALKYL HALIDES
T.O. Olomola, PhD.

Nigeria.
1
Introduction
Organic compounds which have halogen atoms bonded to a carbon atom
are called organohalogens. There are three major classes of organo-
halogen compounds: the alkyl halides, which simply have a halogen
atom bonded to one of the sp3 hybrid carbon atoms of an alkyl group; the
vinyl halides, which have a halogen atom bonded to one of the sp2 hybrid
carbon atoms of an alkene; and the aryl halides, which have a halogen
atom bonded to one of the sp2 hybrid carbon atoms of an aryl group.
The arrangement of groups around the carbon atom in alkyl halides (or
haloalkanes) is tetrahedral. Since halogens are more electronegative than
carbon, the carbon‒halogen bond of alkyl halides is polarized. The
carbon‒halogen bond length increases while the bond strength decreases
down the group. Alkyl halides are used as solvents for relatively non-
polar compounds, and they are used as starting materials in the synthesis
of many compounds.
- +
C
X 2
Alkyl halides simply have one of the H-atoms of an alkane replaced by a
halogen atom, e.g. CH3Cl and CH3CH2CH2I.
Alkyl halides can be classified as primary (1°), secondary (2°), or
tertiary (3°) based on the substitution at the carbon atom bearing the
halogen. If the carbon atom that the halogen is directly attached to is
bonded to not more than one carbon atom, then the alkyl halide is
primary. If the carbon bearing the halogen is also attached to two carbon
atoms, then the alkyl halide is secondary. Similarly, when the carbon
bearing the halogen is attached to three other carbon atoms, then the
carbon is a tertiary carbon and the alkyl halide is tertiary.
HH HC
lH C
H3
H
C CB
r HCCCH H
C
3 CB
r
HH HHH C
H3
1
°a
l
kylh
al
i
d e 2
°a
l
kylh
al
i
d e 3
°a
l
kylh
al
i
d e
3
Nomenclature
Alkyl halides are simply represented as RX with the general formula
CnH2n+1X (for a monohalide) where R is an alkyl group.
Common names are used for simple alkyl halides. E.g.
CH3I – Methyl iodide
CH3CH2Cl – Ethyl chloride
CH3CH2CH2Br – Propyl bromide
Using the IUPAC nomenclature, the halogen group comes first and then
this is followed by the alkane from which the alkyl group is derived.
CH3CHBrCH3 – 2-bromopropane
CH3CH(Cl)CH(CH3)CH2CH3 – 2-chloro-3-methylpentane
When the parent chain has both a halo and alkyl substitutent attached to
it, number the chain from the end nearer the first substituent (halo or
alkyl)
4
Preparation of Alkyl Halides
1. From Alcohols
Alcohols react with a variety of reagents to yield alkyl halides. The
most commonly used reagents are hydrogen halides (order of
reactivity is HI > HBr > HCl, HF is generally unreactive),
phosphorus tribromide and thionyl chloride. Some examples of
these reactions are shown below.
CH3CH2CH2CH2OH (or NaBr, H2SO4)
+ c. HBr CH3CH2CH2CH2Br + H2O
CH3CH2OH + PBr3 CH3CH2Br + H3PO3
OH Cl
+ SOCl2 + SO2 +HCl
5
2. Halogenation of Alkanes
Alkanes react with the first three members of the halogen family
(fluorine, chlorine and bromine) to give a mixture of haloalkanes
and hydrogen halide. Alkanes do not really react with iodine. The
reaction of an alkane with a halogen is a substitution reaction called
halogenation. A halogen atom replaces one or more of the halogen
atoms of the alkane.
CH3 heat,  CH3
H3C C CH3 + Cl2 H3C C CH2Cl
or light, h
CH3 CH3
2,2-dimethylpropane 1-chloro-2,2-dimethylpropane
6
3. Addition of Hydrogen Halides to Alkenes
Hydrogen halides add to the double bond of alkenes. These additions
are sometimes carried out by dissolving the hydrogen halide in a
solvent such as acetic acid or dichloromethane, or by bubbling the
gaseous hydrogen halide directly into the alkene, using the alkene
itself as solvent.
+
H
Br
B
r
In unsymmetrical alkenes, this addition follows the Markovnikov rule
and for cases where HBr is used, the introduction of a peroxide would
result in an anti-Markovnikov addition product.
7
Physical Properties of Alkyl Halides
Alkyl halides generally have low solubility in water but they are
miscible with each other. Dichloromethane (CH2Cl2, also called
methylene chloride), trichloromethane also called chloroform
(CHCl3) and tetrachloromethane (CCl4, also called carbon
tetrachloride) are often used as solvents for not so polar compounds.
Many chloroalkanes have cumulative toxicity and are carcinogenic
and so should only be used in the fumehood.
Iodomethane is the only monohalomethane that is a liquid at room
temperature. Bromoethane and iodoethane are both liquids but
chloroethane is a gas. In general, higer chloro-, bromo-, and
iodoalkanes are all liquids and tend to have boiling points near those
of alkanes of similar molecular weights.
8
Reactions of Alkyl Halides
1. Nucleophilic Substitution: Alkyl halides commonly undergo
nucleophilic substitution reaction. In this type of reaction a
nucleophile, a specie (organic or inorganic, charged or neutral) with an
unshared electron pair, reacts with an alkyl halide (called the
substrate) by replacing the halogen. A substitution reaction takes place
and the halogen substituent, called the leaving group, departs as a
halide ion. The carbon‒halogen bond of the substrate undergoes
heterolysis, and the unshared electron pair of the nucleophile is used
to form a new bond to the carbon atom.
N
u
+
R
XRN
u
+
X
The question then arises: when does the carbon‒halogen bond break?
Does it break at the same time the new bond between the nucleophile
and the carbon forms? Or does the carbon‒halogen bond break
first?
9
Some reactions of alkyl halides include the following:
X+
R O
H R OH+ X
a
lc
oho
l
X+
R N
H3 R N
H2+ H
X
a
min
e
X+
R O
R R OR+ X
e
the
r
X+
R I RI + X
a
lk
ylio
did
e
Other nucleophiles include CN-, RC≡C-, N3-, SH-, RCOO-. To better
understand these reactions of alkyl halides, it is important to understand
the mechanism of the reactions. Does the reaction take place in one step
or more? Which intermediates are formed? Which steps are fast and
which are slow?
10
Mechanism of Nucleophilic Substitution Reaction of Alkyl
Halides
There are two types of possible substitution mechanisms:
A. Unimolecular Mechanism
If the rate equation for a substitution reaction is first order with
respect to one of the reactants (in this case the alkyl halide) in the
slowest step of the reaction called the rate determining step, such a
substitution reaction is called a substitution nucleophilic unimolecular
reaction. A general representation is presented below.
O
v
e
r
al
l
: +
R
B
r O
H R
O
H+B
r
E
l
e
men
t
a
ry
st
e
ps r s
: R
B l
o
w +
RBr
f
a
st
+
ROH R
O
H
rate = k[RBr]
As shown above, the first step involves heterolytic cleavage of the
carbon-bromine bond leading to a carbocation formation.
11
The stability of carbocation (earlier discussed) enhances the reaction.
Thus, the order of reactivity of alkyl halides to SN1 reaction is
3° > 2° > 1° > CH3X
A typical example of an SN1 reaction is
C
H3
CH
3
H
2O
O
ve
rall: H
3CCBr + O
H H
3CCOH+ B
r
C
H3
CH
3
C
H3
C
H3
S
te
ps: s
lo
w
H
3CCBr H
3CC + B
r T
heion
sar
e s
olva
ted(
a n
dsta
biliz
ed)
C
H b
ywate
rmole
cule
s
C
H3 3
C
H3 CH
3
HCC + fa
st HCCOH
3 O
H 3
C
H3 CH
3
12
B. Bimolecular Mechanism
In this case the reaction is second order overall. This means that two
species are involved in the rate determining step of the reaction. This
type of substitution reaction is called a substitution nucleophilic
bimolecular reaction. A general representation is presented below.
O
v
er
al
l: R
CH
2r +O
B H R
CH
2O
H+B
r
R R
R
Br   H
OC +B
r
M
e
ch
an
i
sm: O
H+ OC B
H r
HH H
HH H
t
ran
si
ti
ons
t
ate
r
ate=
k[
R C
HB
2r
][
O H]
In the transition state, a bond between oxygen and carbon is partially

formed and the bond between and the bond between carbon and
bromine is partially broken.
13
For SN2 reactions, it has been experimentally determined that the order
of reactivity is
CH3X > 1° > 2° > 3°
This trend in reactivity is largely due to steric hindrance i.e. the alkyl
groups around the central carbon atom serve as an obstruction to an
incoming group. Thus, primary alkyl halides have the best reactivity in
general.
14
2. Elimination:
Elimination reaction of alkyl halides are important reactions that
compete with substitution reactions. In an elimination reaction the
fragments of some molecule are removed from adjacent atoms of the
reactant. This elimination leads to the introduction of a multiple bond.

XY
C
C
X
Y
Dehydrohalogenation is a widely used method for synthesizing alkenes
and it involves the removal of HX from adjacent atoms of an alkyl
halide. The reaction usually takes place by heating the alkyl halide with
a strong base. Similar to what obtains with substitution reactions,
elimination also involves a leaving group and an attacking Lewis base
that possess and electron pair. The overall transformation leading to the
alkene is called a 1,2-elimination or a β-elimination. Bases used for
dehydrohalogenation include KOH in ethanol, NaOEt in ethanol,
KOBut and NaOH.
15
Chloroalkanes, bromoalkanes and iodoalkanes all undergo elimination
to form alkenes. A general representation of the reaction is:
H
 
C C + + H B+ X
B
Xb ase
E.g.
E
tOH
,55°
C
C
H3CH
C H
3 + N
aOC
2H5 H
3CCC2 +N
H aBr + C
2HO
5 H
H
Br
C
H3 C
H3
HCCBr + N
aOCH E
tOH
,55°
C
2 5 +N
3 aBr + C
2HO
5 H
C
H3 H
3C C
H2
Elimination reactions occur by a variety of mechanisms. With alkyl

halides, the two important ones are closely related to the substitution
cases discussed earlier.
16
Mechanism of Elimination Reaction of Alkyl Halides
There are two types of possible elimination mechanisms:
A. Unimolecular Mechanism
E1 stands for elimination, unimolecular (1st order) reaction mechanism.
E1 eliminations, like SN1 substitutions, begin with unimolecular
dissociation (in the rate determining step), but the dissociation is
followed by loss of a proton from the ꞵ-carbon as a result of a base
abstraction.
C H 3 C H 3
O v e r a ll: H 3 C C C l + H O H 3 C C O H + H 3 O + C l
2
C H 3 C H 3
C H 3 C H 3
M e c h a n is m : s lo w
H 3 C C C l H 3 C C + C l T h e io n s a r e s o lv a te d ( a n d s ta b iliz e d )
C H b y w a te r m o le c u le s
C H 3 3
C H 3 C H 3
H C C fa s t H C C + H O H
3 + O H 3
H C H H C H 2 H
H
Rate = k[RX] 17
E1 and SN1 normally occur in competition, whenever an alkyl halide is
treated in a protic solvent with a nonbasic, poor nucleophile.
Note: The best E1 substrates are also the best SN1 substrates, and
mixtures of products are usually obtained.
E1 reactions are favoured with substrates that can form stable
carbocations, poor nucleophiles (weak bases) and use of polar solvents.
In most unimolecular reactions the SN1 reactions is favoured over the
E1 reaction, especially at low temperatures. Increasing the temperature
of the reaction favours reaction by the E1 mechanism at the expense of
the SN1 mechanism.
18
B. Bimolecular Mechanism
Elimination bimolecular (E2) reactions of alkyl halides have a
transition state for the rate determining step involving both the alkyl
halide and the base. The rate equation is first order in each reactant and
second order overall. A typical example of an E2 reaction is shown
below.
O
ve
rall: C
2HO+
5
C
HC
3 H
Br
C H
3 H
2CC
HC3 +C
H 2HO
5 H+ B
r
M
ec
han
is
m : C
2HO
5 H C
H3 C
2HOH C
5 H3 H C
H3
H H C + CHO H+B
r
2 5
H
H Br H
H B
r H H
Rate = k[CH3CHBrCH3][C2H5O-]
In the transition state, the double bond is partially formed while the
bond between hydrogen and the β-carbon, and the bond between
carbon and bromine are partially broken.
19
Grignard Reagents:
One of the applications of alkyl halides is in their use in the synthesis of
organometallic compounds. Alkyl halides react with some metals in
ether or tetrahydrofuran to form organometallic compounds (such as
organozinc, organolithium and organomagnesium compounds). While
alkyl halides are electrophiles (with the carbon carrying the halide
having a δ+ charge), their organometallic derivatives are nucleophiles
(with the carbon linked to the metal having a δ- charge.
Grignard reagents are organomagnesium compounds with the general
formula RMgX (where X = Cl, Br or I), which are very reactive and
versatile compounds. These reagents are popular in synthetic chemistry
for their usefulness in forming carbon-carbon bonds. A Grignard reagent
is prepared by reacting an alkyl halide with magnesium turnings in dry
ether. These reagents were discovered by French Chemist Victor
Grignard who won the Nobel prize in Chemistry in 1912 for this work.
d
r
y
d
i
e
t
h
yl
e
t
h
e
r
3 C
+
C
H
I
M
g H
M
g
3I
o
r
T
H
F
20
RX can be alkyl, vinyl or aryl halide (Cl, Br or I)
Synthetic applications of Grignard reagent include the following:
a. Alkane formation:
Grignard reagent are very strong bases. They abstract proton from
water, alcohols and terminal alkynes.
HO
2
R
M
g
X RH
R
X
R
M
g
X 
R
R
b. Alcohol formation:
This is arguably the most useful application of Grignard reagents. It
involves the reaction of Grignard reagent with carbonyl compounds.
The general mechanism of the reaction is as presented below:
R R


-
+ hy
d
r
o
l
y
s
es

+
+
R
M
g
X +
O O
M
g
XH
O
3 O
H

-
 Grignard reagents react with formaldehyde to give primary
alcohols
H
C
H
O
+R
C
H
O
2H
R
M
g
X
21
m
e
t
h
a
n
a
l1
°
a
l
c
o
h
ol
 Grignard reagents react with higher aldehydes to give secondary
alcohols
C
H
3
C
H
C
H
+OR
C
H
O
H
R
M
g
X
3
e
t
h
a
nl2
a°
a
l
c
o
h
o
l
 Grignard reagents react with ketones to give tertiary alcohols
OC
H
3
+ R
R
M
g
X
C
O
H
C
H
3
3
°
a
l
c
o
h
ol
 Grignard reagents react with esters to give tertiary alcohols
O R
+
2
R
M
g
X R
'
C
O
H
R
'O
E
t
R
3
°
a
l
c
oh
o
l
 Also, Grignard reagents react with epoxides to give alcohols
O
RMgX + R C C OH
22
c. Ketone formation:
Grignard reagents react with acid chlorides to give ketones.
O O
R
MX+R
g ' C
l R
' R
d. Reaction with carbon(IV) oxide

H
R
MX+ C
g O2 R
CO
OH
Think through and complete the reaction scheme below:

M
g ? ?
R
C
l ? RC
H
OH RC
H
C
2l
2
23
End of Lecture 4
24
TRANSITION METALS
Winston Doherty
CHEM DEPT, OAU Ife
 These are called the inner transition
elements, and they belong here
Electron Configuration of the 1st row
[Ar]4s13d5 additional stability with

completely filled d-orbital
[Ar]4s13d10
additional stability with half-filled d-orbital
Transition metals …. the 1st row
Credit:
Chang: Essential
concepts
METALLIC PROPERTIES &
CATIONS FORMATION
. All are metals
. possess strong metallic bonds
. Loose electron in 4s orbitals
1st & then from the 3d orbitals
Oxidation …most
states of the stable
first-row oxidation
transition numbers
metals. are in red
COLOURED IONS…aqueous solutions of some
transition metal ions
…ions with
partially filled
d-orbitals
tend to be
coloured.
..ions with a d10 (full) or d0 (empty) configuration are colourless

Splitting of d-orbitals
Credit: Blackman
Complexes & Ligands
Ligand Formula Name of ligand
Chloride Cl- Chloro
Cyamide CN- Cyano
Hydroxide OH- Hydroxo
Oxide O2- Oxo
Water H2O Aqua
Ammonia NH3 ammine

Ligands Monodentate
Bidentate
Ligands…classified by the number of lone pairs
…. Multidentate & bidentate ligands lead to more
stable complexes.
SHAPES….governed by number of ligands
around the central ion.
…based on electron pair repulsion theory
…change of ligand can affect the shape.
Coordination Number
Coordination No. Shape Example
…..a change of
ligand can affect
6 (six fold) Octahedral [Co(NH3)6]3+ [Co(H2O)6]2+ the coordination
number.
4 (fourfold) Tetrahedral [CuCl4]2-
Square Planar [Ni(CN)4]2-
2 (twofold) Linear [Ag(NH3)3]+
If monodentate ligands are present, it will equal the

number of ligands
Catalysis
Example: Oxidation of SO2 in the Contact Process is catalysed by vanadium(V) oxide (V2O5)
Step 1 V2O5(s) + SO2(g) V2O4(s) + SO3(g)
Step 2 V2O4(s) + ½O2(g) V2O5(s)
Overall S2O4(s) + ½O2(g) SO3(s)

Magnetic properties.. types: para magnetism, diamagnetism and
ferromagnetism.
Para magnetism: magnetic lines of force pass through the substance rather than through a
vacuum; paramagnetic substance is attracted into a magnetic field…. caused by presence
of unpaired electrons. Diamagnetism: magnetic lines of force pass through the
vacuum rather than through the substance; thus, diamagnetic substance is
repelled by a magnetic field and hence tends to set itself at right angles to the
field. all electrons are paired. Ferromagnetism is a form of para magnetism..the
moments on individual atoms become aligned & all point in the same direction.
Fe, Co and Ni are known example.

Thank you
….all the best
in your
exams…
THE DESCRIPTIVE CHEMISTRY
OF THE MAIN GROUP VI
Winston Doherty PhD, MRACI
CChem
Chemistry Department, OAU Ife
• Group 16 of the
• Also called the periodic table
chalcogens
Group 16: oxygen (O), sulfur (S), selenium (Se),

tellurium (Te), polonium (Po)
• Group 16
Selenium Se8
Sulphur S8
Tellurium Te
𝑯𝒆 𝟐𝑺𝟐 𝟐𝑷𝟒
𝑵𝒆 𝟑𝑺𝟐 𝟑𝑷𝟒
𝑨𝒓 𝟑𝒅𝟏𝟎 𝟒𝑺𝟐 𝟒𝑷𝟒
𝑲𝒓 𝟒𝒅𝟏𝟎 𝟓𝑺𝟐 𝟓𝑷𝟒
𝑿𝒆 𝟒𝒇𝟏𝟒 𝟓𝒅𝟏𝟎 𝟔𝑺𝟐 𝟔𝑷𝟒

Oxidation States
Oxidation States
Oxygen shows -2 oxidation states in general except in OF2 and O2F2

IONISATION ENERGY (I.E)
The I.E of the elements
decreases down the
group.
“▰ EA decreases down the grp from S to
ELECTRON AFFINITY (EA)
Po
Due to increase in atomic size
▰ O’s EA is lower than that of S
because of the small size of O
NON-METALLIC
CHARACTER DECREASES The elements
DOWN THE GRP transition from non-
metallic Oxygen and
Sulphur to Polonium
METALLIC CHARACTER
which is radioactive
INCREASES DOWN THE GRP and metallic.
Due to decrease of IE from
Oxygen to Polonium
Melting & Boiling points
increase with an increase in

atomic number
O’s bpt is lower than that of S; O is diatomic (O2),
& sulphur is octatomic (S8).
ALLOTROPY..all elements exhibit allotropy
. oxygen exists only . sulphur has
as two gaseous many allotropes,
allotropes (O2 and all of which are
O3) insulators;
. the stable forms . polonium is a

of selenium and metallic conductor
tellurium are & exists in two
semiconductors; forms
CATENATION
 Oxygen & Sulphur show the property of catenation
 Both O & S tend to form chains of identical atoms
 Chains of S atoms in persulphides, polythionic acids in S8
molecule. O gives polyoxides similar to poly sulphides by S
H2O2, H – O – O – H; H2S2, H-S-S-H H2S3, H -S-

S-S-H
REACTIVITIES: Fomation of Hydrides
All d elements form the hydride of the type H2M where M=O, S, Se, Te, Po.
2H2 + O2 → H2O
FeS + H2SO4 → FeSO4 + H2S
K2Se + H2SO4 → K2SO4 + H2Se

Preparation: H2O is prepared by burning H2 in O2; & H2S, H2Se and H2Te
by d action of acids on metal sulphides, selenides and tellurides.

PROPERTIES OF THE HYDRIDES
Shape: Bent
Bond angle H2O > H2S < H2Se < H2Te
b.pt 373K 213K 232K 269K
Intermolecular H-bonding; Increase in van der Waals Forces

PROPERTIES OF THE HYDRIDES
Acidic nature: H2O < H2S < H2Se < H2 Te
WHY: H-M (M= O, S, Se, Te) bond length increases down d grp.
Therefore, d bond dissociation energy decreases down d grp.
Thermal stability: H2O < H2S < H2Se < H2Te < H2Po
Reducing character : H2O < H2S < H2Se < H2Te < H2Po
..all the elements form oxides
FORMATION OF OXIDES
The oxides of the
elements in the same . e.g. SO2
oxidation state become
less acidic as we go
(acidic); TeO2
down the group. (amphoteric))
Monoxides MO – TRIOXIDES: S, Se
except Se, all other and Te form the
elements give MO trioxides of MO3
(SO, TeO, PoO) type.
REDUCING CHARACTER
The reducing Reason : O has a
character of the strong + field that
dioxides decreases attracts the hydroxyl
as we go down the group & the removal
group. of H+ becomes easy
Reason: SeO2 has a

polymeric chain
SO2 is a gas, SeO2
structure, whereas
is solid SO2 forms discrete
units.
FOMATION OF HALIDES
They form Fluorine is more

binary halides. electronegative
than oxygen
Fluorine
compounds with e.g OF2 used
oxygen are called as rocket fuel
fluoride of oxygen
FORMATION OF HALIDES
MX2, MX4 and MX6 M = Grp 16 elements
Halide's stability decreases in the order F->Cl->Br->I-
because M-X bond length increases with an increase in
size. Dihalides are Sp3 hybridised, are tetrahedral in
shape.
FOMATION OF MX6 (M = S, Se, Te)
Among hexa
halides, M show maximum
fluorides most covalency of six
stable due to using their d-
steric reasons. orbitals.
MF6 - colourless MF6 are stable; stability
gases, M is Sp3d2 decreases from SF6 to
hybridized & TeF6 due to the
structure - increase in size from S
octahedral. to Te atom.
TETRAHALIDES
…prepared by direct rxn between the element and X2 molecules.
𝑀 + 2𝑋2 → 𝑀𝑋4
.
𝑀 = 𝑆, 𝑆𝑒, 𝑇𝑒
𝑺𝑭𝟒 𝒊𝒔 𝒂 𝒈𝒂𝒔, 𝑺𝒆𝑭𝟒 𝒊𝒔 𝒂 𝒍𝒊𝒒𝒖𝒊𝒅 𝒘𝒉𝒊𝒍𝒆 𝑻𝒆𝑭𝟒 𝒊𝒔 𝒔𝒐𝒍𝒊𝒅

OXYGEN …preparation
OXIDES
…the compounds of oxygen & other elements
.
OXIDES
…the compounds of oxygen & other elements
.
OZONE …. Prepared by
…passing a silent electric discharge through pure & dry
oxygen; 10-15% converted to ozone
3O2(g) ⇌2O3; ∆𝑯 = +𝟏𝟒𝟐𝑲𝑱 𝒎𝒐𝒍−𝟏

.
…structure: angular; bonds: equal length due to resonance
SULPHUR …..sulphur exhibits allotropy
…at 96oC (transition temp) both forms are stable.
Rhombic ⇌ Monoclinic
…2 forms have S8 molecules & has crown shape
..another allotrope of sulphur
…cyclo S6 adopts a chair form
… S2 is formed at high temp (~727oC). S2 is paramagnetic due
to unpaired electrons in antibonding pie orbitals like O2

SULPHURIC ACID…most important acid in
chemical industry
…manufactured in contact process
…rxn is exothermic; low temp & high pressure favour the rxn
SO3(g) + H2SO4 →H2S2O7 (Oleum)
H2S2O7 + H2O → 2H2SO4 96-98% purity

…acid is dibasic/diprotic, strong dehydrating agent, moderate
oxidizing agent for S, C, P etc.

CARBOHYDRATES
By:
Dr. I. O. Otemuyiwa
Dept of Chemistry
Obafemi Awolowo University, Ile-Ife, Nigeria
1
Carbohydrates are polyhydroxy aldehydes or ketones, or substances that yield such compounds on hydrolysis. Most
substances of this class have empirical formulas suggesting that they are carbon "hydrates," in which the ratio of
C : H : O is 1: 2 : 1. For example, the empirical formula of glucose is C6H12O6, which can also be written (CH2O)6 or
C6(H2O)6. Although many common carbohydrates conform to the empirical formula (CH2O)n, others do not; some
carbohydrates also contain nitrogen, phosphorus, or sulfur
There are three major size classes of carbohydrates: monosaccharides, oligosaccharides, and polysaccharides (the word
"saccharide" is derived from the Greek sakkharon, meaning "sugar").
Monosaccharides, or simple sugars, consist of a single polyhydroxy aldehyde or ketone unit. The most abundant
monosaccharide in nature is the six carbon sugar D-glucose.
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Monosaccharides
Monosaccharides are colorless, crystalline solids that are freely soluble in water but insoluble in nonpolar
solvents. Most have a sweet taste. The backbone of monosaccharides is an unbranched carbon chain in which all
the carbon atoms are linked by single bonds. One of the carbon atoms is double-bonded to an oxygen atom to
form a carbonyl group; each of the other carbon atoms has a hydroxyl group. If the carbonyl group is at an end of
the carbon chain, the monosaccharide is an aldehyde and is called an aldose; if the carbonyl group is at any other
position, the monosaccharide is a ketone and is called a ketose. The simplest monosaccharides are the two three-
carbon trioses: glyceraldehyde, an aldose, and dihydroxyacetone, a ketose.
Monosaccharides with four, five, six, and seven carbon atoms in their backbones are called, respectively,
tetroses, pentoses, hexoses, and heptoses. There are aldoses and ketoses of each of these chain lengths:
aldotetroses and ketotetroses, aldopentoses and ketopentoses, and so on.
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Reactions of Monosaccharides
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Ester and Ether Formation
The -OH groups on a monosaccharide can be readily converted to esters and ethers. Esterification can be done with
an acid chloride or acid anhydride, while treatment with an alkyl halide leads to the ether
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Summary of reactions
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Formation of glycosides
The hydroxyl group that is attached to the anomeric carbon atom (i.e., the carbon containing the aldehyde or keto
group) of carbohydrates in solution has unusual reactivity, and derivatives, called glycosides, can be formed;
glycosides formed from glucose are called glucosides. It is not possible for equilibration between the α- and β-
anomers of a glycoside in solution (i.e., mutarotation) to occur. The reaction by which a glycoside is formed
involves the hydroxyl group (―OH) of the anomeric carbon atom (numbered 1) of both α and β forms of D-
glucose—α and β forms of D-glucose are shown in equilibrium in the reaction sequence—and the hydroxyl group
of an alcohol (methyl alcohol in the reaction sequence); methyl α-D-glucosides and β-D-glucosides are formed as
products, as is water.
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Disaccharides
Disaccharides are a specialized type of glycoside in which the anomeric hydroxyl group of one sugar has
combined with the hydroxyl group of a second sugar with the elimination of the elements of water.
Sucrose, or common table sugar, its world production had amounted to more than 170 million tons annually. The
unusual type of linkage between the two anomeric hydroxyl groups of glucose and fructose means that neither a
free aldehyde group (on the glucose moiety) nor a free keto group (on the fructose moiety) is available to react
unless the linkage between the monosaccharides is destroyed; for this reason, sucrose is known as a
nonreducing sugar.
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Maltose, or malt sugar, is a disaccharide formed by a dehydration reaction between two glucose molecules.
Lactose is a disaccharide consisting of the monomers glucose and galactose.
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Polysaccharides
A long chain of monosaccharides linked by glycosidic bonds is known as a polysaccharide (poly– = “many”). The
chain may be branched or unbranched, and it may contain different types of monosaccharides. The molecular
weight may be 100,000 daltons or more depending on the number of monomers joined. Starch, glycogen,
cellulose, and chitin are primary examples of polysaccharides.
Starch is the stored form of sugars in plants and is made up of a mixture of amylose and amylopectin (both
polymers of glucose).
Starch is made up of glucose monomers that are joined by α 1-4 or α 1-6 glycosidic bonds. The numbers 1-4 and
1-6 refer to the carbon number of the two residues that have joined to form the bond. As illustrated in Figure below
amylose is starch formed by unbranched chains of glucose monomers (only α 1-4 linkages), whereas amylopectin
is a branched polysaccharide (α 1-6 linkages at the branch points)
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Cellulose is the most abundant natural biopolymer. The cell wall of plants is mostly made of cellulose; this
provides structural support to the cell. Wood and paper are mostly cellulosic in nature. Cellulose is made up of
glucose monomers that are linked by β 1-4 glycosidic bonds
As shown in Figure below, every other glucose monomer in cellulose is flipped over, and the monomers are
packed tightly as extended long chains. This gives cellulose its rigidity and high tensile strength—which is so
important to plant cells. While the β 1-4 linkage cannot be broken down by human digestive enzymes, herbivores
such as cows, koalas, buffalos, and horses are able, with the help of the specialized flora in their stomach, to
digest plant material that is rich in cellulose and use it as a food source.
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Thank you
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FATS AND OILS
By:
Dr. I. O. Otemuyiwa
Dept of Chemistry
Delta Nomenclature
Chemists use Delta Nomenclature, but nutritionists are more focused on the Omega system which
focuses on the nutritional value of the fatty acid. For Delta Nomenclature one needs to know 3 things:
Number of carbons in the fatty acid
Number of double bonds
Number of carbons from the carboxylic acid (alpha) end to the first carbon in the double bond(s)
Number of carbons in the fatty acid = 18

Number of double bonds = 1
Number of carbons from the carboxylic acid end to the first carbon in the double bond = 9
Omega Nomenclature
The Omega Nomenclature is almost exactly the same as the Delta Nomenclature; the only difference is that
carbons are counted from the methyl (omega) end instead of the carboxylic acid end, and the omega symbol is
used instead of the delta symbol.
For Omega Nomenclature one needs to know 3 things:
Number of carbons in the fatty acid
Number of double bonds
Number of carbons from the methyl end (aka Omega end) to the first carbon in the double bond closest to the
methyl end
Fatty acid where the double bond is at the ninth carbon from the end (omega)
Table: Common names of fatty acids[1]
Omega Name Common Name
4:0 Butyric Acid
12:0 Lauric Acid
14:0 Myristic Acid
16:0 Palmitic acid
18:0 Stearic Acid
20:0 Arachidic Acid
24:0 Lignoceric Acid
18:1 (n-9) Oleic Acid
18:2 (n-6) Linoleic Acid
18:3 (n-3) Alpha-linolenic Acid
20:4 (n-6) Arachidonic Acid
20:5 (n-3) Eicosapentanoic Acid
22:6 (n-3) Docosahexanoic Acid

Fats and oils are called triglycerides (or triacylcylgerols) because they are esters composed of three fatty acid units joined
to glycerol, a trihydroxy alcohol:
If all three OH groups on the glycerol molecule are esterified with the same fatty acid, the resulting ester is called
a simple triglyceride. However, a typical triglyceride obtained from naturally occurring fats and oils contains two or three
different fatty acid components and is thus termed a mixed triglyceride.
A triglyceride is called a fat if it is a solid at 25°C; it is called an oil if it is a liquid at that temperature. These differences in
melting points reflect differences in the degree of unsaturation and number of carbon atoms in the constituent fatty acids.
Triglycerides obtained from animal sources are usually solids, while those of plant origin are generally oils. Therefore, we
commonly speak of animal fats and vegetable oils.
 Physical Properties of Fats and Oils
Contrary to what you might expect, pure fats and oils are colorless, odorless, and tasteless. The characteristic colors,
odors, and flavors that we associate with some of them are imparted by foreign substances that are lipid soluble and have
been absorbed by these lipids. For example, the yellow color of butter is due to the presence of the pigment carotene; the
taste of butter comes from two compounds—diacetyl and 3-hydroxy-2-butanone—produced by bacteria in the ripening
cream from which the butter is made.
Fats and oils are lighter than water, having densities of about 0.8 g/cm3. They are poor conductors of heat and electricity
and therefore serve as excellent insulators for the body, slowing the loss of heat through the skin.
Chemical Reactions of Fats and Oils
Saponification - The hydrolysis of fats and oils in the presence of a base is used to make soap and is
called saponification.
Hydrogenation – fat and oil react with hydrogen in presence of Nickel catalyst to form saturated fat called Margarine
Oxidation/Antioxidants
Oxidation (exposure to air) causes rancidity in fats over time. Fats and oils that are in contact with moist air at room
temperature eventually undergo oxidation and hydrolysis reactions that cause them to turn rancid, acquiring a
characteristic disagreeable odor. This is made worse by combination with certain metals, such as copper.
One cause of the odor is the release of volatile fatty acids by hydrolysis of the ester bonds. Butter, for example, releases
foul-smelling butyric, caprylic, and capric acids. Microorganisms present in the air furnish lipases that catalyze this
process. Hydrolytic rancidity can easily be prevented by covering the fat or oil and keeping it in a refrigerator.
Another cause of volatile, odorous compounds is the oxidation of the unsaturated fatty acid components, particularly the
readily oxidized structural unit in polyunsaturated fatty acids, such as linoleic and linolenic acids. One particularly
offensive product, formed by the oxidative cleavage of both double bonds in this unit, is a compound
called malonaldehyde.
This oxidation can be minimized by the addition of antioxidants. Antioxidants are compounds whose affinity for oxygen is
greater than that of the lipids in the food; thus they function by preferentially depleting the supply of oxygen absorbed into
the product. Some oils contain natural antioxidants, such as tocopherols (vitamin E is one kind), but these are often
destroyed during the processing. As a result, manufacturers add synthetic antioxidants to retard rancidity. BHA and BHT
are synthetic antioxidants commonly used by fat manufacturers.
 Cleansing action of Soap
Dirt and grime usually adhere to skin, clothing, and other surfaces by combining with body oils, cooking fats, lubricating
greases, and similar substances that act like glues. Because these substances are not miscible in water, washing with water
alone does little to remove them. Soap removes them, however, because soap molecules have a dual nature. One end, called
the head, carries an ionic charge (a carboxylate anion) and therefore dissolves in water; the other end, the tail, has a
hydrocarbon structure and dissolves in oils. The hydrocarbon tails dissolve in the oil; the ionic heads remain in the aqueous
phase, and the soap breaks the oil into tiny soap-enclosed droplets called micelles, which disperse throughout the solution.
The droplets repel each other because of their charged surfaces and do not coalesce. With the oil no longer “gluing” the dirt
to the soiled surface (skin, cloth, dish), the soap-enclosed dirt can easily be rinsed away.
Chemistry of Amines
By:
Dr. I. O. Otemuyiwa
Dept of Chemistry
1
Amines are organic compounds which contain and are often actually based on one or more atoms of nitrogen.
Structurally amines resemble ammonia in that the nitrogen can bond up to three hydrogens, but amines also have
additional properties based on their carbon connectivity. In an amine, one or more of the hydrogen atoms from
ammonia are replaced by organic substituents like alkyl (alkane chain) and aryl (aromatic ring) groups.
Amine Primary Amine Secondary Amine Tertiary Amine
Types of amines
Amines can be either primary, secondary or tertiary, depending on the number of carbon-containing groups that are
attached to them.
If there is only one carbon-containing group (such as in the molecule CH3NH2) then that amine is considered
primary. Two carbon-containing groups makes an amine secondary, and three groups makes it tertiary.
Utilizing the lone electron pair of nitrogen, it is sometimes energetically favored to use the nitrogen as a nucleophile
and thus bind a fourth carbon-containing group to the amine. In this case, it could be called a quaternary
ammonium ion.
2
General properties
Hydrogen bonding significantly influences the properties of primary and secondary amines as well as the
protonated derivatives of all amines. Thus the boiling point of amines is higher than those for the corresponding
phosphines (compounds containing phosphorus), but generally lower than the corresponding alcohols. Alcohols,
or alkanols, resemble amines but feature an -OH group in place of NR2. Since oxygen is more electronegative
than nitrogen, RO-H is typically more acidic than the related R2N-H compound.
Methyl, dimethyl, trimethyl, and ethyl amines are gases under standard conditions. Most common alkyl amines
are liquids, and high molecular weight amines are, quite naturally, solids at standard temperatures. Additionally,
gaseous amines possess a characteristic ammonia smell, while liquid amines have a distinctive “fishy” smell.
Most aliphatic amines display some solubility in water, reflecting their ability to form hydrogen bonds. Solubility
decreases relatively proportionally with the increase in the number of carbon atoms in the molecule – especially
when the carbon atom number is greater than six. Aliphatic amines also display significant solubility in organic
solvents, especially in polar organic solvents. Primary amines react readily with ketone compounds (such
as acetone), however, and most amines are incompatible with chloroform and also with carbon tetrachloride as
solvent solutions. 3
Properties as bases
When evaluating the basicity of a nitrogen-containing organic functional group, the central question we need to
ask ourselves is: how reactive (and thus how basic) is the lone pair on the nitrogen? In other words, how much
does that lone pair want to break away from the nitrogen nucleus and form a new bond with a hydrogen?
Like ammonia, amines act as bases and are reasonably strong (see the provided table for some examples of
conjugate acid Ka values). The basicity of amines varies by molecule, and it largely depends on:
 The availability of the lone pair of electrons from nitrogen
 The electronic properties of the attached substituent groups (e.g., alkyl groups enhance the basicity, aryl groups diminish
it, etc.)
 The degree of solvation of the protonated amine, which depends mostly on the solvent used in the reaction
The nitrogen atom of a typical amine features a lone electron pair which can bind a hydrogen ion (H+) in order
to form an ammonium ion — R3NH+. The water solubility of simple amines is largely due to the capability for
hydrogen bonding that can occur between protons on the water molecules and these lone pairs of electrons. 4
Comparing the basicity of alkyl amines to ammonia
Because alkyl groups donate electrons to the more electronegative nitrogen. The inductive effect makes the
electron density on the alkylamine’s nitrogen greater than the nitrogen of ammonium. Correspondingly, primary,
secondary, and tertiary alkyl amines are more basic than ammonia.
Comparing the basicity of alkylamines to amides

With an alkyl amine the lone pair electron is localized on the nitrogen. However, the lone pair electron on an
amide are delocalized between the nitrogen and the oxygen through resonance. This makes amides much less
basic compared to alkylamines.
In fact, when and amide is reacted with an acid, the protonation occurs at the carbonyl oxygen and not the
nitrogen. This is because the cation resulting from oxygen protonation is resonance stabilized. The cation
resulting for the protonation of nitrogen is not resonance stabilized.
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Reactions of Amines
Due to the unshared electron pair, amines can act as both bases and nucleophiles.
Reaction with acids
When reacted with acids, amines donate electrons to form ammonium salts.
Reaction with acid halides

Acid halides react with amines to form substituted amides.
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Aldehydes and ketones react with primary amines to give a reaction product (a carbinolamine) that dehydrates to
yield aldimines and ketimines (Schiff bases).
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Reaction with nitrous acid
Nitrous acid is unstable and must be prepared in the reaction solution by mixing sodium nitrite with acid.
Primary amines react with nitrous acid to yield a diazonium salt, which is highly unstable and degradates into a
carbocation that is capable of reaction with any nucleophile in solution. Therefore, reacting primary amines with
nitrous acid leads to a mixture of alcohol, alkenes, and alkyl halides.
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Amino acids and Proteins
By:
Dr. I. O. Otemuyiwa
Dept of Chemistry
Obafemi Awolowo University, Ile-Ife, Nigeria 1
Proteins, from the Greek proteios, meaning first, are a class of organic compounds containing Carbon, Hydrogen, Oxygen
and Nitrogen. They are present in and vital to every living cell. In the form of skin, hair, callus, cartilage, muscles, tendons
and ligaments, proteins hold together, protect, and provide structure to the body of a multi-celled organism. In the form of
enzymes, hormones, antibodies, and globulins, they catalyze, regulate, and protect the body chemistry. In the form of
hemoglobin, myoglobin and various lipoproteins, they effect the transport of oxygen and other substances within an
organism. Proteins are generally regarded as beneficial, and are a necessary part of the diet of all animals. Humans can
become seriously ill if they do not eat enough suitable protein, the disease kwashiorkor being an extreme form of protein
deficiency.
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Amino acid structure and its classification
An amino acid contains both a carboxylic group and an amino group. Amino acids that have an amino
group bonded directly to the alpha-carbon are referred to as alpha amino acids.
Every alpha amino acid has a carbon atom, called an alpha carbon, Cα; bonded to a carboxylic
acid, –COOH group; an amino, –NH2 group; a hydrogen atom; and an R group that is unique for
every amino acid.
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The n-carboxylic acid group of amino acids is a weak acid, meaning that it releases hydrogen
(such as a proton) at moderate pH values. In other words, carboxylic acid groups (-CO2H) can be
deprotonated to become negative carboxylates (COO - ). The negatively charged carboxylate ion
predominates at pH values greater than the pKa of the carboxylic acid group (meaning that for the
20 common α- amino acids it is about 2.2). In a complementary fashion, the amine of amino acids
is a weak base, meaning that it accepts a proton at moderate pH values. In other words, amino
groups (NH2-) can be protonated to become positive ammonium groups (+NH3-). The positively
charged ammonium group predominates at pH values less than the pKa of the ammonium group
(meaning that for the 20 common α-amino acids it is about 9.4).
Because all amino acids contain amine and carboxylic acid functional groups, they share
amphoteric properties. Below pH 2.2, the predominant form will have a neutral carboxylic acid
group and a positive - ammonium ion (net charge +1), and above pH 9.4, a negative carboxylate
and neutral -amino group (net charge -1). But at pH between 2.2 and 9.4, an amino acid usually
contains both a negative carboxylate and a positive -ammonium group and this result in a zero net
charge. This molecular state is known as a zwitterion, from the
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The Isoelectric Point
The isoelectric point, pI, is the pH of an aqueous solution of an amino acid (or peptide) at which the molecules on
average have no net charge. In other words, the positively charged groups are exactly balanced by the negatively
charged groups. For simple amino acids such as alanine, the pI is an average of the pKa's of the carboxyl (2.34) and
ammonium (9.69) groups. Thus, the pI for alanine is calculated to be: (2.34 + 9.69)/2 = 6.02, the experimentally
determined value. If additional acidic or basic groups are present as side-chain functions, the pI is the average of the
pKa's of the two most similar acids. To assist in determining similarity we define two classes of acids. The first
consists of acids that are neutral in their protonated form (e.g. CO2H & SH). The second includes acids that are
positively charged in their protonated state (e.g. -NH3+). In the case of aspartic acid, the similar acids are the alpha-
carboxyl function (pKa = 2.1) and the side-chain carboxyl function (pKa = 3.9), so pI = (2.1 + 3.9)/2 = 3.0. For
arginine, the similar acids are the guanidinium species on the side-chain (pKa = 12.5) and the alpha-ammonium
function (pKa = 9.0), so the calculated pI = (12.5 + 9.0)/2 = 10.75.
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Examples of some α-amino acids
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Classification of Amino acids
Nonpolar Amino Acids

 Ala: Alanine Gly: Glycine Ile: Isoleucine Leu: Leucine Met: Methionine Trp: Tryptophan
 Phe: Phenylalanine Pro: Proline Val: Valine
Polar Amino Acids
 Cys: Cysteine Ser: Serine Thr: Threonine Tyr: Tyrosine Asn: Asparagine Gln: Glutamine
Polar Basic Amino Acids (Positively Charged)
 His: Histidine Lys: Lysine Arg: Arginine
Polar Acidic Amino Acids (Negatively Charged)
 Asp: Aspartate Glu: Glutamate
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Essential Amino acids
An essential amino acid or indispensable amino acid (or proteinogenic amino acid) is an amino acid that cannot be
synthesized de novo by the organism, but must be supplied in its diet. The essential amino acids that must enter the body
through diet are histidine, isoleucine, leucine. lysine. Methionine and cysteine (or sulphur amino acids), phenylalanine
and tyrosine (or aromatic amino acids), threonine, tryptophan, and valine.
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Synthesis of α-Amino Acids
1) Amination of alpha-bromo-carboxylic acids. The bromoacids are prepared from carboxylic acids by reaction with Br2 +
PCl3. Although this direct approach gave mediocre results when used to prepare simple amines from alkyl halides, it is
more effective for making amino acids, thanks to the reduced nucleophilicity of the nitrogen atom in the product.
Nevertheless, more complex procedures that give good yields of pure compounds are often chosen for amino acid synthesis.
2) The Strecker synthesis, assembles an alpha-amino acid from ammonia (the amine precursor), cyanide (the carboxyl
precursor), and an aldehyde. This reaction (shown below) is essentially an imino analog of cyanohydrin formation. The
alpha-amino nitrile formed in this way can then be hydrolyzed to an amino acid by either acid or base catalysis
9
Reactions of α-Amino Acids
1. Carboxylic Acid Esterification
Amino acids undergo most of the chemical reactions characteristic of each function, assuming the pH is adjusted to an appropriate value.
Esterification of the carboxylic acid is usually conducted under acidic conditions, as shown in the two equations written below. Under
such conditions, amine functions are converted to their ammonium salts and carboxylic acids are not dissociated.
Esterification of α-amino acids in the presence of methanol yields a stable ammonium salt. The amino ester formed by neutralization of
this salt is unstable, due to acylation of the amine by the ester function.
The second reaction illustrates benzylation of the two carboxylic acid functions of aspartic acid, using p-toluene - sulfonic acid as an
acid catalyst. Once the carboxyl function is esterified, zwitterionic species are no longer possible and the product behaves like any 1º-
amine.
10
1. The Ninhydrin Reaction
In addition to these common reactions of amines and carboxylic acids, common alpha-amino acids, except proline, undergo a
unique reaction with the triketohydrindene hydrate known as Ninhydrin. Among the products of this unusual reaction is a
purple colored imino derivative, which provides as a useful color test for these amino acids, most of which are colorless.
11
Peptide bonds
Amino acids are linked together by ‘amide groups’ called peptide bonds.
During protein synthesis, the carboxyl group of amino acid at the end of the growing polypeptide
chain reacts with the amino group of an incoming amino acid, releasing a molecule of water. The
resulting bond between the amino acids is a peptide bond.
Amide linkages between amino acids are known as peptide bonds, and the product of peptide bond formation between two
amino acids is called a dipeptide. The peptide chain may be extended to incorporate three amino acids in a tripeptide, four
in a tetrapeptide, and so on. Polypeptides contain many amino acid units. If the amine and carboxylic acid functional
groups in amino acids join together to form amide bonds, a chain of amino acid units, called a peptide, is formed
12
PROTEINS
Proteins can be classified as:

(a) Simple proteins. On hydrolysis they yield only the amino acids and occasional small carbohydrate compounds.
Examples are: albumins, globulins, glutelins, albuminoids, histones and protamines.
(b) Conjugated proteins. These are simple proteins combined with some non-protein material in the body. Examples are:
nucleoproteins, glycoproteins, phosphoproteins, haemoglobins and lecithoproteins.
(c) Derived proteins. These are proteins derived from simple or conjugated proteins by physical or chemical means.
Examples are: denatured proteins and peptides.
Proteins can also be classified as
(i) Fibrous proteins; these are keratins, collagens and elastins. They are relatively insoluble, quaternary structured proteins
that play important roles in the physical structure of organisms.
(ii) Globular proteins are more soluble in aqueous solutions, and are generally more sensitive to temperature and pH
change than are their fibrous counterparts.
13
Structural Classifications of Proteins
Primary Structure
Primary Structure describes the unique order in which amino acids are linked together to form a protein. Proteins are
constructed from a set of 20 amino acids.
14
Secondary Structure
Secondary Structure refers to the coiling or folding of a polypeptide chain that gives the protein its 3-D shape. There are
two types of secondary structures observed in proteins. One type is the alpha (α) helix structure. This structure resembles
a coiled spring and is secured by hydrogen bonding in the polypeptide chain. The second type of secondary structure in
proteins is the beta (β) pleated sheet. This structure appears to be folded or pleated and is held together by hydrogen
bonding between polypeptide units of the folded chain that lie adjacent to one another.
15
16
Tertiary Structure
Tertiary Structure refers to the comprehensive 3-D structure of the polypeptide chain of a protein. There are several types of
bonds and forces that hold a protein in its tertiary structure. They are:
(i) Hydrophobic interactions. The "R" group of the amino acid is either hydrophobic or hydrophilic. The amino acids with
hydrophilic "R" groups will seek contact with their aqueous environment, while amino acids with hydrophobic "R" groups
will seek to avoid water and position themselves towards the center of the protein.
(ii) Hydrogen bonding.
(iii) ionic bonding or electrostatic interaction
(iv) disulfide bridge.
17
Tertiary Structure of Proteins
18
Quaternary Structure
When multiple polypeptide chain subunits come together, then the protein attains its quaternary
structure.
•An example for quaternary structure is hemoglobin. The hemoglobin carries oxygen in the blood
and is made up of four subunits, two each of the α and β types
19
Denaturation and protein folding
Each protein has its own unique shape. If the temperature or pH of a protein's environment is
changed, or if it is exposed to chemicals, these interactions may be disrupted, causing the
protein to lose its three-dimensional structure and turn back into an unstructured string of
amino acids.
When a protein loses its higher-order structure, but not its primary sequence, it is said to be
denatured. Denatured proteins are usually non-functional
The denaturation process can be achieved by any one of the following methods: increasing
temperature, changing pH, using denaturants (i.e.urea, guanidine hydrochloride, beta-
mercaptoethanol, dithiothreitol), inorganic salts (i.e lithium bromide, potassium thiocyanate,
sodium iodide), organic solvents and (i.e. formamide, dimethylformamide, dichloro- and
trichloroacetic acids and their salts), detergents (i.e. sodium dodecyl sulphate), high pressure and
ultrasonic homogenization.
20
Carboxylic acids
By:
Dr. I. O. Otemuyiwa
Dept of Chemistry
When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are
called carboxylic acids.
Carboxylic acids are classified according to the substituent that is bonded to the carboxyl carbon:
Aliphatic acids have an alkyl group bound to the carboxyl group.
An aromatic acid has an aryl group bound to the carboxyl group.
A carboxylic acid donates protons by the heterolytic cleavage of the O-H bond, generating a carboxylate ion.
Physical Properties of Carboxylic Acids
Carboxyl groups exhibit very strong hydrogen bonding. A given carboxylic acid molecule form two
hydrogen bonds to another carboxylic acid molecule, producing a “dimer”, a complex with a mass
twice that of a single molecule.
Compounds with carboxyl groups have higher boiling points than alcohols. This is because the
carboxyl groups hydrogen bond more strongly than alcohols
Carboxyl groups make molecules very soluble in water because the group can strongly hydrogen
bond with water.
Preparation of Carboxylic Acids
Carboxylic acids are easily by oxidation of primary alcohols and aldehydes. When the oxidation
process begins with an alcohol it is difficult to stop at the aldehyde stage of oxidation.
Oxidation of primary alcohol to carboxylic acid.
CH3CH2CH2OH ---> CH3CH2CHO ---> CH3CH2COOH

primary alcohol aldehyde acid
Nomenclature
IUPAC formulation
The root name is based on the longest continuous chain of carbon atoms bearing the carboxyl group.
The -e is replaced by -oic acid.
The chain is numbered starting with the carboxyl carbon atom.
The carboxyl group takes priority over any other functional groups previously discussed.
E.g.
Acidity
Carboxylic acids can dissociate in aqueous solution into carboxylate ions and protons.
The equilibrium constant for this process is Ka, and more frequently we talk in terms of pKa
The reason why carboxylic acids are much more acidic than alcohols is because the carboxylate anion is much more stable
than the alkoxide anion.
Both alcohols and carboxylic acids are acidic since their respective O-H bonds can be broken heterolytically, giving a
proton and an oxygen anion. The difference lies in the fact that the carboxylate anion has the negative charge spread out
over two oxygen atoms, whereas the alkoxide has the negative charge localized on a single oxygen atom.
Esterification
 A carboxylic acid and an alcohol will form an ester and water
Reaction with Alkalis- The reaction of carboxylic acids with alkalies will lead to the formation of corresponding salts and
water.
Reaction with Carbonates and Bicarbonates

Carboxylic acids undergo decomposition reaction with carbonates and bicarbonates leading to the formation of respective salts,
water, and carbon dioxide gas. This reaction can also help in testing the presence of carboxyl group. Carboxylic acids undergo
reaction with a saturated solution of sodium bicarbonate produce effervescence due to the release of CO2 gas. However, most
phenols do not release effervescence with an aqueous NaHCO3 solution. Thus the reaction of bicarbonate with carboxylic acids
helps in distinguishing between phenols and carboxylic acids.
Reaction with Carbonates and Bicarbonates
Carboxylic acids undergo decomposition reaction with carbonates and bicarbonates leading to the formation of respective salts,
water, and carbon dioxide gas. This reaction can also help in testing the presence of carboxyl group. Carboxylic acids undergo
reaction with a saturated solution of sodium bicarbonate produce effervescence due to the release of CO2 gas. However, most
phenols do not release effervescence with an aqueous NaHCO3 solution. Thus the reaction of bicarbonate with carboxylic acids
helps in distinguishing between phenols and carboxylic acids.
However, most phenols do not release effervescence with an aqueous NaHCO3 solution. Thus the reaction of bicarbonate with
carboxylic acids helps in distinguishing between phenols and carboxylic acids.
Formation of Esters (Esterification)

Warming carboxylic acids with alcohols in the presence of a concentrated sulphuric acid or dry hydrochloric acid produces
esters having a fruity smell.
Decarboxylation
Distillation of soda lime (NaOH + CaO) with sodium salts of carboxylic acids result in decarboxylation reaction thereby
forming alkanes.
CHM102: ALDEHYDES & KETONES
T.O. Olomola, PhD.

Nigeria.
1
Introduction
Carbonyl compounds are ubiquitous in nature, and they are of
importance to organic chemistry, biology and biochemistry. Proteins,
carbohydrates and nucleic acids all contain the carbonyl group.
The carbonyl, though sp2 hybridized with a bond angle of 120°, is rather
different from an alkene because O-atom is more electronegative than
carbon, hence the C=O bond is polar. In addition, the carbonyl C=O is
also shorter and stronger than the alkene double bond.
+ -
C O
Aldehydes and ketones are carbonyl compounds attached to groups that
cannot be replaced by a nucleophile. When the carbonyl is linked to one
alkyl group and a hydrogen, it is an aldehyde and when the carbonyl is
connected to two alkyl groups (or a ring residue) it is a ketone.
R R
CO C O
H 
R
2
a
l
deh
y
de k
et
one
Both aldehydes and ketones have the general formula of CnH2nO.
Aldehydes are represented generally as RCHO and the functional group
is terminal, while the non terminal ketone is represented as RCORʹ. The
polarization of the carbonyl group contributes to the properties and
reactivity of ketones and aldehydes.
Other carbonyl containing compounds are carboxylic acids, esters,

anhydrides, acyl halides and amides.
3
Nomenclature
a. Aldehydes
- Trivial names derived from the corresponding carboxylic acids
4
- IUPAC nomenclature
5
b. Ketones
- Trivial naming can be used such that both alkyl groups are named
followed by ketone.
6
- IUPAC nomenclature
7
Preparation
1. Oxidation of primary alcohols gives aldehydes while oxidation of
secondary alcohols gives ketones.
Jones reagent (K2Cr2O7 / dil. H2SO4) can be used for oxidation of

primary alcohols with 4 carbon atoms or less, while Collins reagent
(CrO3˖2 pyridine in CH2Cl2) or PCC (pyridinium chlorochromate)
in DCM may be used for alcohols with longer C-atoms. A mild
oxidant is required to avoid oxidation all the way to the acid.
For secondary alcohols, Jones reagent, basic KMnO4 or H2CrO4

may be used. 8
2. Ozonolysis of alkenes
Depending on the original alkene substitution pattern, ozonolysis
followed by reduction cleaves an alkene double bond to give
ketones and aldehydes.
CH3 CH3 1) O3 in CH 2Cl2 CH3 CH3
C=C C O +O C
2) CH3SCH3 + DMSO
H CH3 H CH3
or Zn/HOAc
DMS
O
O O O
O O O O
CH3 CH3
C=C H O
H
H CH3
ozonide
9
3. Hydration of alkynes: Hydroboration-oxidation of an alkyne gives
anti-Markovnikov addition of water across the triple bond. Di
(secondary isoamyl)borane, called disiamylborane, is used, since this
bulky borane cannot add twice across the triple bond. On oxidation of
the borane, the unstable enol quickly tautomerizes to the aldehyde.
OH
1) disiamyl borane
CH3CH2C CH CH3CH2CH=CH2
2) H2O2, NaOH
an enol
B O
H CH3CH2CH2CH
(sia)2BH an aldehyde
10
Sulphuric acid and mercuric ion catalysed hydration of a terminal
alkyne gives the Markovnikov addition of water across the triple bond
leading to the formation of an unstable enol that tautomerizes to the
ketone. Internal alkynes can also be hydrated but a mixture of
products often results.
OH
HgSO 4, H2SO4
CH3CH2C CH CH3CH2C=CH2
H2O
an enol
O
CH3CH2CCH3
a ketone
11
4. Friedel-Crafts Acylation
Friedel-Crafts alkylation is a good way for synthesizing diaryl
ketones or alkyl aryl ketones.
12
The Gatterman-Koch synthesis is a variant of the Friedel-Crafts
acylation in which carbonmonoxide and HCl generate an
intermediate that reacts like formyl chloride.
O
CH
CO, HCl
AlCl 3/CuCl
benzene or activated benzene needed
in situ preparation of formyl chloride
O
C O + HCl HCCl
13
Physical Properties of Aldehydes & Ketones
Neither aldehydes nor ketones possess the ability to H-bond with other
molecules like themselves. Consequently, boiling points for aldehydes
and ketones are lower than for alcohols of similar molar mass.
The C-O double bond in these molecules is polar, so dipole-dipole
forces do exist. As a result, their boiling points tend to be higher than
for alkanes of similar molar mass.
Water molecules can interact (H-bond) with the non-bonding pairs of
the carbonyl group oxygen atom, enabling aldehydes and ketones that
have small carbon chain components to be water-soluble.
In general, the greater the carbon chain length, the lower the water-
solubility (molecule becomes less polar).
14
15
Reactions of Aldehydes & Ketones
In general, aldehydes are more reactive than ketones.
1. Oxidation: Aldehydes can be oxidized easily to carboxylic acids,
but ketones are resistant to oxidation.
Tollen’s reagent test is used as a standard way of distinguishing

between aldehydes and ketones. Aldehydes gives a positive silver
mirror deposit, while ketones do not.
16
2. The haloform reaction (base-catalysed halogenation of methyl
ketones) is an example of a reaction occuring at an α-C to a carbonyl.
When the halogen is iodine, the haloform product (iodoform) is a

solid that separates out as a yellow precipitate. This iodoform test
identifies methyl ketones, which halogenate three times, then
lose CI3 to give iodoform.
17
3. Reduction: Sodium borohydride (NaBH4) is a simple reducing
agent that reduces ketones to secondary alcohols and aldehydes to
primary alcohols. Lithium aluminium hydride (LiAlH4) is a more
powerful reducing agent capable of reducing more than just the
ketone or aldehyde groups (such as carboxylic acid, ester, amide,
nitrile).
Catalytic hydrogenation with Ni is also a possible reaction, but double

and triple bonds will also react under these conditions.
18
Deoxygenation involves the replacement of the
carbonyl oxygen by 2 hydrogen atoms leading to an
alkane. This can take place under two reaction
conditions:
 Clemmenson reduction: this reduction method
works for compounds that are not sensitive to acid.
19
Wolff-Kishner reduction: for compounds that are acid
sensitive.
20
4. Nucleophilic addition

O + OH
O H3O


Nu: Nu Nu
Basic nucleophiles: RMgX, RLi, LiAlH 4, NaBH4, RC CNa

-
Nonbasic nucleophiles: CN
a. Formation of alcohols
b. Formation of cyanohydrins
O OH
CH C H
HCN, (KCN trace amt.)
CN
+ enant.
Mandelonitrile
H in defense glands of
O millipede A. corrugata
CH
CN 21
c. Formation of acetals
O + HO OCH3
H , CH3OH +
H , CH3OH CH3O OCH3
hemiacetal acetal
O CH3CH2O OCH2CH3
+
excess CH3CH2OH, H + H2O
d. Formation of imines
22
23
End of Lecture 5
24
By:
Dr. I. O. Otemuyiwa
Dept of Chemistry
1
Alcohols or Alkanols
Alcohols or Alkanols are organic compounds in which a hydrogen atom of an aliphatic carbon is replaced
with a hydroxyl group
Structure and classification of alcohols
One way of classifying alcohols is based on which carbon atom is bonded to the hydroxyl group. If this carbon is primary
(1°, bonded to only one other carbon atom), the compound is a primary alcohol.
A secondary alcohol has the hydroxyl group on a secondary (2°) carbon atom, which is bonded to two other carbon
atoms.
A tertiary alcohol has the hydroxyl group on a tertiary (3°) carbon atom, which is bonded to three other carbons.
Alcohols are referred to as allylic or benzylic if the hydroxyl group is bonded to an allylic carbon atom (adjacent to a C=C
double bond) or a benzylic carbon atom (next to a benzene ring), respectively
2
3
Nomenclature
Common names
The common name of an alcohol combines the name of the alkyl group with the word alcohol. If the alkyl group is complex,
the common name becomes awkward and the IUPAC name should be used. Common names often incorporate obsolete
terms in the naming of the alkyl group; for example, amyl is frequently used instead of pentyl for a five-carbon chain.
Using the IUPAC system, the name for an alcohol uses the -ol suffix with the name of the parent alkane, together with a
number to give the location of the hydroxyl group. The rules are summarized in a three-step procedure:
*Name the longest carbon chain that contains the carbon atom bearing the ―OH group. Drop the final -e from the alkane
name, and add the suffix -ol.;
*Number the longest carbon chain starting at the end nearest the ―OH group, and use the appropriate number, if necessary,
to indicate the position of the ―OH group; and
4
*Name the substituents, and give their numbers as for an alkane or alkene.
Using the IUPAC system, the name for an alcohol uses the -ol suffix with the name of the parent alkane, together with a
number to give the location of the hydroxyl group. The rules are summarized in a three-step procedure:
*Name the longest carbon chain that contains the carbon atom bearing the ―OH group. Drop the final -e from the alkane
name, and add the suffix -ol.;
*Number the longest carbon chain starting at the end nearest the ―OH group, and use the appropriate number, if necessary,
to indicate the position of the ―OH group; and
*Name the substituents, and give their numbers as for an alkane or alkene.
5
Physical Properties of Alcohol
Most of the common alcohols are colourless liquids at room temperature. Methyl alcohol, ethyl alcohol, and isopropyl
alcohol are free-flowing liquids with fruity odours. The higher alcohols—those containing 4 to 10 carbon atoms—are
somewhat viscous, or oily, and they have heavier fruity odours. Some of the highly branched alcohols and many
alcohols containing more than 12 carbon atoms are solids at room temperature.
The Boiling Point of Alcohols
Alcohols generally have higher boiling points in comparison to other hydrocarbons having equal molecular masses. This
is due to the presence of intermolecular hydrogen bonding between hydroxyl groups of alcohol molecules. In general,
the boiling point of alcohols increases with an increase in the number of carbon atoms in the aliphatic carbon chain.
On the other hand, the boiling point decreases with an increase in branching in aliphatic carbon chains the Van der
Waals forces decreases with a decrease in surface area. Thus, primary alcohols have a higher boiling point.
The oxygen atom of the strongly polarized O―H bond of an alcohol pulls electron density away from the hydrogen
atom. This polarized hydrogen, which bears a partial positive charge, can form a hydrogen bond with a pair of
nonbonding electrons on another oxygen atom.
6
2. Solubility of Alcohols
The solubility of alcohol in water is governed by the hydroxyl group present. The hydroxyl group in alcohol is involved in
the formation of intermolecular hydrogen bonding. Thus, hydrogen bonds are formed between water and alcohol molecules
which make alcohol soluble in water. However, the alkyl group attached to the hydroxyl group is hydrophobic in nature.
Thus, the solubility of alcohol decreases with the increase in the size of the alkyl group. Alcohols with higher molecular
weights tend to be less water-soluble, because the hydrocarbon part of the molecule, which is hydrophobic (“water-hating”),
is larger with increased molecular weight. Because they are strongly polar, alcohols are better solvents than hydrocarbons for
ionic compounds and other polar substances.
7
. The Acidity of Alcohols
Alcohols react with active metals such as sodium, potassium etc. to form the corresponding alkoxide. These reactions of
alcohols indicate their acidic nature. The acidic nature of alcohol is due to the polarity of –OH bond. The acidity of alcohols
decreases when an electron-donating group is attached to the hydroxyl group as it increases the electron density on the oxygen
atom. Thus, primary alcohols are generally more acidic than secondary and tertiary alcohols.
Acidity of alcohols: formation of alkoxides
Alcohols are weak acids. The most acidic simple alcohols (methanol and ethanol) are about as acidic as water, and most other
alcohols are somewhat less acidic.
A strong base can deprotonate an alcohol to yield an alkoxide ion (R―O−). For example, sodamide (NaNH2), a very strong
base, abstracts the hydrogen atom of an alcohol. Metallic sodium (Na) or potassium (K) is often used to form an alkoxide by
reducing the proton to hydrogen gas.
8
Preparation of alcohols
 By catalytic reaction of carbon monoxide (CO) with hydrogen gas (H2) under high temperature and pressure.
Methanol is synthesized commercially by this method
 Hydration of alkenes
The addition of water (hydration) across the double bond of an alkene yields an alcohol. In most cases, water adds in the
direction that places the new hydroxyl group on the more highly substituted end of the double bond according to
the Markovnikov rule, as in acid-catalyzed hydrations. (The more highly substituted end of the double bond is the one that is
bonded to more carbon atoms.)
9
 By Fermentation
Ethanol (ethyl alcohol) has been produced since prehistoric times, mostly through the fermentation of fruit juices. Many
different sources can provide the sugars and starches that are broken down to simpler compounds during fermentation.
Ethanol is called grain alcohol because it is often made from grains, such as corn (maize), wheat, rye, and barley. The grain
is first boiled in water to produce the mash, which is incubated with malt (sprouted barley) to yield the wort. Malt provides
an enzyme (diastase) that converts starches in the grain to the sugar maltose. The wort is incubated with brewer’s yeast,
which secretes the enzyme maltase to convert maltose to glucose and the enzyme zymase to convert glucose to ethanol. Two
of the six carbon atoms in glucose are oxidized to carbon dioxide (CO2); this oxidation provides energy to the yeast cells.
10
Chemical Properties of Alcohols
Oxidation of Alcohol
•Alcohols undergo oxidation in the presence of an oxidizing agent to produce aldehydes and ketones which upon further
oxidation give carboxylic acids.
Secondary alcohols are easily oxidized without breaking carbon-carbon bonds only as far as the ketone stage. No further
oxidation is seen except under very stringent conditions. Tertiary alcohols cannot be oxidized at all without breaking carbon-
carbon bonds, whereas primary alcohols can be oxidized to aldehydes or further oxidized to carboxylic acids.
Chromic acid (H2CrO4, generated by mixing sodium dichromate, Na2Cr2O7, with sulfuric acid, H2SO4) is an effective
oxidizing agent for most alcohols. It is a strong oxidant, and it oxidizes the alcohol as far as possible without breaking
carbon-carbon bonds. Chromic acid oxidizes primary alcohols to carboxylic acids, and it oxidizes secondary alcohols to
ketones. Tertiary alcohols do not react with chromic acid under mild conditions. 11
Dehydration to alkenes
Dehydrations are most commonly carried out by warming the alcohol in the presence of a strong dehydrating acid, such as
concentrated sulfuric acid
Most alcohol dehydrations take place by the mechanism shown below Protonation of the hydroxyl group
allows it to leave as a water molecule. The species that remains has a carbon atom with only three bonds
and a positive charge and is called a carbocation. This intermediate species can be stabilized by loss of
a proton from a carbon atom adjacent to the positively charged carbon ion, giving the alkene.
12
Because they involve carbocation intermediates, alcohol dehydrations go more quickly and easily if they form relatively
stable carbocations. More highly substituted carbocations are more stable (3° > 2° > 1°); therefore, more highly substituted
alcohols undergo dehydration more readily than less highly substituted alcohols (3° > 2° > 1°). If more than one alkene
can be formed in a dehydration, the major product is usually the product with the most highly substituted double bond
(Saytzeff’s rule)
13
Dehydration to ethers
Under carefully controlled conditions, simple alcohols can undergo intermolecular dehydration to give ethers. This reaction
is effective only with methanol, ethanol, and other simple primary alcohols, but it is the most economical method for
making ethyl ether (also known as diethyl ether), an important industrial solvent.
Esterification
Alcohols can combine with many kinds of acids to form carboxylic esters that is the ester of an alcohol and a carboxylic
acid. The reaction, called Fischer esterification, is characterized by the combining of an alcohol and an acid (with acid
catalysis) to yield an ester plus water.
14
Substitution to form alkyl halides
Alkyl halides are often synthesized from alcohols, in effect substituting a halogen atom for the hydroxyl group. Hydrochloric
(HCl), hydrobromic (HBr), and hydroiodic (HI) acids are useful reagents for this substitution, giving their best yields with
tertiary alcohols. Thionyl chloride (SOCl2), phosphorus tribromide (PBr3), and phosphorus triiodide (generated
from phosphorus, P, and molecular iodine, I2) are also useful for making alkyl chlorides, bromides, and iodides, respectively.
15

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CHM 102

DR. MRS L.M.DUROSINMI

• Light Pink ------Hydrated Mn2+ salts

• CdS, is yellow. All the precipitates, except for HgS, are

• The action of ammonia is also useful in differentiating

• This group of cations includes ions that form hydroxides

• Cations : Fe2+, Fe3+, Al3+, and Cr3+.

• The group is determined by making a solution of the salt in

• a gelatinous white precipitate indicates Al3+; and

• a green precipitate indicates Cr3+ or Fe2+. These two

• Cations left after separating groups 1-5 are considered to be

• These are Mg2+, Li+, Na+ and K+.

• All the ions are distinguished by flame color:

• lithium gives a red flame, sodium gives bright yellow (even

o consists of CO32− , HCO3−, CH3COO−, S2−, and NO−

o The reagent for Group 1 anions is dilute hydrochloric acid

o The milkiness disappears on passing an excess of the gas

• The 2nd group of anions consist of Cl−, Br−, I−, NO−

• The group reagent for Group 2 anion is concentrated

• Bromides and iodides are confirmed by the layer test. A sodium

• The anions consist of SO42− , Phosphate and borate anions;

• They react neither with concentrated nor diluted H2SO4.

• Sulfates give a white precipitate of BaSO4 with BaCl2 which

• Phosphates give a yellow crystalline precipitate upon

• Borates give a green flame characteristic of ethyl

 Many atoms become stable when their valence shell is

 The atoms do so by gaining, losing, or sharing

combine with any other metal.

due to the fact that they already have low

 It is important to note that a molecule will only be

 Chemical bonds are attractive forces that hold/bind

 Chemical bonds form because they lower the potential energy

2 Americans – G.N. Lewis & Irving Langmuir

4. Electrons are transferred or shared to the extent that each

The type of chemical bond formed varies in strength and

These types of bonds in chemical bonding are

• Ionic solids are generally characterized by high

• Covalent bonds are a class of chemical bonds

Pi bonds are a weaker type of covalent

• Polar covalent bond is a separation of electric charge

• A bond that results from unequal sharing of electrons.

• Another example of such polar molecule is water.

• Formed when the lone or non-bonding pairs of

In odd-electron species, there is:

i. At least one unpaired electron in the structure.

The presence of unpaired electrons causes odd

• The NO molecule has 11 valence electrons.

• The central atom has incomplete Octet,

• BF3 readily combines with ammonia, NH3 to

• Phosphorus in group V with five electrons in the

• In PCL5 , all the 5Cl atoms are bonded to the central

• The phenomenon of octet expansion are found

• There are molecules and ions for which

• Oxygen gas commonly occurs as diatomic

• Ozone, O3, is one such substances for which a

• Experimental evidence indicates that the two

• Ozone -Triatomic molecule. There are two

• The arrows in this formula indicate that the

• Therefore neither of the two structures can be