BASIC ORGANIC CHEMISTRY CHG 1201 5 CU

First part.
Course outline:
- Introduction to Organic Chemistry

- Covalent compounds versus ionic compounds

- Application of organic Chemistry in everyday life.

- Determination of molecular formula of organic compounds

- Separation and purification of organic compounds

- Identification and structural determination of organic compounds outlining several

spectroscopic techniques.

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Introduction to Organic Chemistry
This is the branch of chemistry that deals with the study of compounds of carbon. All organic
compounds contain carbon together with one or more other elements such as hydrogen, oxygen,
chlorine, nitrogen and sulphur. These organic compounds range from simple molecules such as
methane, ethene, ethyne, to giant molecules such as Deoxyribonucleic acid (DNA), Ribonucleic
acid (RNA), rubber, cotton, drugs, insecticides, explosives and photographic films- of which all
these compounds are of great importance in everyday life.

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Uniqueness of Carbon in Organic Compounds
Carbon behaves differently from the rest of the group members due:
➢ Small atomic radius

➢ High electronegativity

➢ Lack of vacant orbital

Some of the properties in which Carbon differs from the rest of the members include:
➢ It forms a stable multiple bonds with itself and with other non-metals, as seen in
alkenes, alkynes, carbonyl carbons and so on.

➢ Carbon can form a number of hydrocarbons because it can catenate. Catenation is

the ability of the element to form bonds between atoms of the same element.

➢ It forms gaseous oxides unlike other members and so on.

➢ Some carbon compounds can exist in isomeric forms.

➢ The ability of carbon to form both chain and cyclic compounds (in which the chain
of atoms is joined end to end to form a ring) based upon either carbon atoms alone
or carbon atoms in combination with those of other nonmetals (e.g., oxygen, sulfur,
nitrogen) and either upon single- or multiple-bond arrangements

Characteristic Properties of Organic Compounds

Most organic compounds are:
i. Covalently bonded and generally gases, volatile liquids and low melting point
solids with few elements such as carbon, hydrogen, Sulphur, nitrogen and halogens.

ii. Low melting and boiling point compounds.

iii. Generally insoluble in water except those with polar functional groups such as
OH, COOH, SO3H

iv. The reactions are generally slow although some are explosive and most reactions
require catalysts.

Covalent Compounds

Covalent bonds are characterized by the sharing of electrons between two or more atoms. These
bonds mostly occur between nonmetals or between two of the same (or similar) elements. Two
atoms with similar electronegativity will not exchange an electron from their outermost shell; the

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atoms instead share electrons so that their valence electron shell is filled. Examples of compounds
that contain only covalent bonds are methane (CH4), carbon monoxide (CO), and iodine
monobromide (IBr).

Properties of Covalent Compounds

▪ Most covalent compounds have relatively low melting points and boiling points.
While the ions in an ionic compound are strongly attracted to each other, covalent
bonds create molecules that can separate from each other when a lower amount of energy
is added to them. Therefore, molecular compounds usually have low melting and boiling
points.
▪ Covalent compounds usually have lower enthalpies of fusion and vaporization than
ionic compounds.
The enthalpy of fusion is the amount of energy needed, at constant pressure, to melt one
mole of a solid substance. The enthalpy of vaporization is the amount of energy, at constant
pressure, required to vaporize one mole of a liquid. On average, it takes only 1% to 10%
as much heat to change the phase of a molecular compound as it does for an ionic
compound.
▪ Covalent compounds tend to be soft and relatively flexible.
This is largely because covalent bonds are relatively flexible and easy to break. The
covalent bonds in molecular compounds cause these compounds to take form as gasses,
liquids, and soft solids. As with many properties, there are exceptions, primarily when
molecular compounds assume crystalline forms.
▪ Covalent compounds tend to be more flammable than ionic compounds.
Many flammable substances contain hydrogen and carbon atoms which can undergo
combustion, a reaction that releases energy when the compound reacts with oxygen to
produce carbon dioxide and water. Carbon and hydrogen have comparable
electronegativies so they are found together in many molecular compounds.
▪ When dissolved in water, covalent compounds don't conduct electricity. Ions are
needed to conduct electricity in an aqueous solution. Molecular compounds dissolve into
molecules rather than dissociate into ions, so they typically do not conduct electricity very
well when dissolved in water.
▪ Many covalent compounds don't dissolve well in water.
There are many exceptions to this rule, just as there are many salts (ionic compounds) that
don't dissolve well in water. However, many covalent compounds are polar molecules that
do dissolve well in a polar solvent, such as water. Examples of molecular compounds that
dissolve well in water are sugar and ethanol. Examples of molecular compounds that don't
dissolve well in water are oil and polymerized plastic.

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Ionic Compounds

Ionic bonding occurs when there is a large difference in electronegativity between two atoms. This
large difference leads to the loss of an electron from the less electronegative atom and the gain of
that electron by the more electronegative atom, resulting in two ions. These oppositely charged
ions feel an attraction to each other, and this electrostatic attraction constitutes an ionic bond.

Ionic bonding occurs between a nonmetal, which acts as an electron acceptor, and a metal, which
acts as an electron donor. Metals have few valence electrons, whereas nonmetals have closer to
eight valence electrons; to easily satisfy the octet rule, the nonmetal will accept an electron donated
by the metal. More than one electron can be donated and received in an ionic bond. Some examples
of compounds with ionic bonding include NaCl, KI, and MgCl2.

Properties of ionic Compounds

The properties of ionic compounds relate to how strongly the positive and negative ions attract
each other in an ionic bond. Iconic compounds also exhibit the following properties:

▪ They form crystals.

Ionic compounds form crystal lattices rather than amorphous solids. Although molecular
compounds form crystals, they frequently take other forms plus molecular crystals
typically are softer than ionic crystals. At an atomic level, an ionic crystal is a regular
structure, with the cation and anion alternating with each other and forming a three-
dimensional structure based largely on the smaller ion evenly filling in the gaps between
the larger ions.
▪ They have high melting points and high boiling points. High temperatures are required
to overcome the attraction between the positive and negative ions in ionic compounds.
Therefore, a lot of energy is required to melt ionic compounds or cause them to boil.
▪ They have higher enthalpies of fusion and vaporization than molecular compounds.
Just as ionic compounds have high melting and boiling points, they usually have enthalpies
of fusion and vaporization that can be 10 to 100 times higher than those of most molecular
compounds. The enthalpy of fusion is the heat required melt a single mole of a solid under
constant pressure. The enthalpy of vaporization is the heat required for vaporize one mole
of a liquid compound under constant pressure.
▪ They are hard and brittle. Ionic crystals are hard because the positive and negative ions
are strongly attracted to each other and difficult to separate, however, when pressure is
applied to an ionic crystal then ions of like charge may be forced closer to each other. The
electrostatic repulsion can be enough to split the crystal, which is why ionic solids also are
brittle.
▪ They conduct electricity when they are dissolved in water.
When ionic compounds are dissolved in water the dissociated ions are free to conduct

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 electric charge through the solution. Molten ionic compounds (molten salts) also conduct
electricity.
▪ They're good insulators.
Although they conduct in molten form or in aqueous solution, ionic solids do not conduct
electricity very well because the ions are bound so tightly to each other.

Assignment:

Read on the applications of Organic chemistry in everyday life

Electrophiles and Nucleophiles

Electrophiles are species which are electron loving since they are electron deficient while
Nucleophiles are species which are electron rich

Examples of Electrophiles and Nucleophiles include:

+
NO2 , H+, Cl+, Br+,R3C+ and RN2+
Electrophiles:
- - - -
Nucleophiles: H2O, ROH,RO , OH, Br CN and NH3
Hydrocarbons
These compounds that contain carbon and hydrogen as the only elements present.
They are classified as:
a) Saturated hydrocarbons

These are hydrocarbons that contain a carbon- carbon single bond e.g. in Alkanes.
b) Unsaturated hydrocarbons

These are hydrocarbons that contain multiple bonds between the carbon atoms e.g. Alkenes
Further classification includes:
c) Aliphatic Hydrocarbons

These are hydrocarbons that contain low carbon-hydrogen ratio. Usually on burning, they burn
with a non-sooty flame.
d) Aromatic hydrocarbons

These are hydrocarbons that contain a high carbon- hydrogen ratio. Usually on burning, they burn
with a sooty flame. These compounds are usually considered as derivatives of benzene.

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N.B Also Alicyclic hydrocarbons are hydrocarbons in which carbon atoms are arranged in the
ring but with no aromatic character.

Functional Groups and Homologous Series

Homologous series is a series of compounds with similar chemical properties and same functional
groups differing from the successive member by CH2.
The characteristics of homologous series include;

• Member of a homologous series can be represented by a general formula e.g. CnH2n+2 for
Alkanes, CnH2n for Alkenes

• Each member of a series has a similar method of preparation

• Members in a given series has a similar chemical properties to each other

• As a series is ascended down, a methylene group is added to each successive member therefore
physical properties such as boiling and melting points change slightly.

• Several homologous series are regarded as alkane derivatives since the hydrogen atom in the
alkane is replaced by a functional group

Functional group is atom or group of atoms which impart specific chemical properties to the
chemical compounds containing them regardless of the nature of the hydrocarbon part of the
molecule.
Generally Organic compounds are classified based upon the functional group because compounds
having the same functional groups have similar chemical properties.
The table below shows some of the examples of functional groups:

Name Structural formula Examples

Alkane RH or CnH2n+2 CH3CH2CH3
Alkenes RCH=CH2 or CnH2n CH3CH=CH2
Alkynes RC CR
or Cn H2n-2 CH3C CCH3

Halogen compounds RCH2X (x=Cl, Br and I) CH3CH2Cl

Alcohols RCH2OH or CnH2n+1OH CH3CH2OH
Carbonyl compounds Aldehydes: RCHO or CH3CH2CHO
CnH2n+1CHO
CH3COCH3

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 Ketones: RCOR or
CnH2n+2CO
Carboxylic acids RCH2COOH or CH3COOH
CnH2n+1COOH
Amines RCH2NH2or CH3CH2NH2,CH3NHCH3
CnH2n+1COOH
Ethers ROR or CnH2n+1O CH3CH2OCH3

CHEMICAL REACTIONS

In chemical reactions, the reactants molecules that are attacked are called Substrate whereas the
general term given to the attacking substrate is called a Reagent. Substrates and reagents usually
interact to yield the products involving redistribution of electrons.

Generally, there are two ways in which a covalent bond can be broken include:

(a) Homolytic cleavage

In this type, the bond is broken symmetrically and each atom remains with one electron to
form a radical. Example includes

These types of reactions are usually catalyzed by:

• Ultraviolet light or short wavelength light or sunlight

• High temperatures

• Peroxide

(b) Heterolytic cleavage

In this kind of the reactions, the bonds are broken unsymmetrically generating cations and anions.
If the molecule contains different atoms with different electronegativity, the tendency of ions
formation differs. These breakages usually take place in solvents of high ionizing power which is
catalyzed by ionic polar catalysts.

Example include: If A is more electronegative than B, then

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 B A A- + B+

Types of Organic Chemical Reactions

Organic reactions are usually initiated by Electrophiles or Nucleophiles or free radical attack upon
the substrate. These reactions include:
(a) Substitution or Displacement reactions
These reactions involve the direct displacement of an atom or group by another atom or group.
The number of atoms displaced depends on the nature of the reactants and conditions under which
the reaction is carried out.
Generally, they are represented as;
H H
H H

Y + Z H C C Z +Y
H C C

H H
H H

e.g.
NaOH (aq)
CH3CH2Cl CH3CH2OH + NaCl
Heat

Substitution reactions are divided into two classes:

(i) Nucleophilic substitution reaction (SN).
These are reactions whereby electron rich species simply displaces an atom or group of atoms.
These reactions are undergone by Alkyl halides.
(ii) Electrophilic substitution reaction (SE)
These are reactions where by electron deficient group displaces an atom. These reactions are
undergone by Benzene where hydrogen atom is replaced by an electron deficient group
According to the number of species involved in the formation of the activated complex in the rate
determining step, Nucleophilic substitution reaction is divided into two:
(i) Nucleophilic substitution unimolecular (SN1) where a single species is involved
in the rate determining step.
(ii) Nucleophilic substitution Bimolecular (SN2) where two species are involved are
involved in the rate determining step.

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(b) Elimination reactions
These are reactions involve the removal of atoms or groups of atoms from two adjacent atoms to
form a multiple bond or unsaturated compound.
These reactions are usually encountered to yield alkenes and alkynes
Generally, they are represented as;
H H
H

H C C H H C C H + YZ

Y Z H

e.g.
Conc.H2SO4
CH3CH2OH H2C CH2 + H2O
o
180 C

Elimination reaction is also divided into two types based upon the number of species involved in
the formation of activated complex in the rate determining step.
i. Elimination unimolecular (E1) e.g., dehydrohalogenation and dehydration of 30 Alkyl
halides and Alcohols respectively.

ii. Elimination bimolecular (E2) e.g., dehydrohalogenation and dehydration of 20 Alkyl

halides and Alcohols.

(c) Addition reactions

These are reactions where by the attacking reagent simply adds across the unsaturated bond of the
reactant to saturated product.
These reactions are usually the reverse of the elimination reactions and the unsaturated reactants
act as Nucleophiles and consequently more vulnerable to attack by Electrophiles.
These are reactions are generally represented as:
Y Z

YZ H C H
H2C CH2 C

H H

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Example includes

HBr

Br

Addition reactions are divided into classes:

(i) Electrophilic addition reactions (AE)

These are reactions where the electron loving species simply adds itself to unsaturated compound
e.g., addition reactions of alkenes and alkynes.
(ii) Nucleophilic addition reactions (AN)
These are reactions where the electron rich species simply adds itself to the unsaturated bond of
the bond e.g., addition reactions of carbonyl compounds
(d) Rearrangement reactions
These are reactions which involve the migration of an atom or group from one site to another
within the same molecule. It involves the migration of a functional group from one position to
another within the same molecule
Example includes

RCHCH CH2 RCH CHCH2 Br

Br

Mechanism of Organic Reactions

Mechanisms of reaction are sequence steps by which the reactions take place from start to the end.
The mechanism is worked out from a study of the kinetics of the reactions. Other method includes
spectroscopy and use of radioactive isotopes.

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ISOMERISM
This is the existence of different compounds with the same molecular formulae but different
structural formulae.
Compounds with same molecular formulae but different structural formulae are known as Isomers.
Isomerism is divided into two classes:
(a) Structural Isomerism
This is the type of isomerism which shows the sequence in which the atoms in a molecule are
bonded or linked.
It is divided into three classes:
(i) Chain Isomerism. This is the type of structural isomerism where by the isomers differ in
the carbon chain. The isomers usually have the same functional group and belong to the same
homologous series.
It can be divided into classes’ i.e., Straight chain and branch chain
Example included: Q has molecular formula C4H10, write down possible chain structural
formula of Q. Since the M.F. is C4H10 isomers are:

CH3CH2CH2CH3 and CH3CHCH3

CH3

(ii) Positional Isomerism. This is the isomerism where the substituent groups are in different
positions in the same carbon skeleton. The isomers are chemically similar because they possess
the same functional groups

CH3CH2CH CH2 and CH3CH CHCH3

CH3CH2CH2OH and CH3CHCH3

OH

(iii) Functional Isomerism. This is the isomerism where by the isomers in different
homologous series have different functional groups.
Examples include:
(a) A compound Q has Molecular formula C2H6O
 The isomers are CH3CH2OH (from Alcohol) and CH3OCH3 (from ether)

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 (b) A compound W has molecular formulaC3H6O

 The isomers are CH3COCH3 (from Ketones) and CH3CH2CHO (from

Aldehydes)
(c) A compound Z has molecular formula C4H8O2
 The isomers are CH3CH2CH2COOH (from Carboxylic acid) and
CH3COOCH2CH3 (from Esthers)
(b) Stereoisomerism
This is the type of isomerism where by the compounds have the same molecular formula and
same structural formula but differ in the spatial arrangement of the bonds.
Stereoisomerism is divided into two classes:
(i) Cis-trans Isomerism (Geometrical Isomerism)
This occurs in compounds in which free rotation is prevented by the presence of multiple
bonds, a ring or steric factors.
Geometrical Isomers differ in spatial arrangement giving rise to cis isomers which has
identical atoms or groups on the same side of the multiple bonds and a trans isomer which
has the atoms or groups in opposite side.
Examples include:
H HOOC
COOH H

C
C
and
C
C
H COOH
H COOH
Trans-isomers
Cis-isomers

(ii) Optical Isomerism

This occurs in compounds with four atoms or groups attached to the same carbon such that the
isomers obtained are not super imposable on the mirror images.
These isomers which are not super imposable are referred as to as Enantiomers and the structures
are said to be chiral.

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Example includes:
Mirror

H
H

C
C
HO CH2CH3
CH3CH2 OH
CH3 CH3

Object Image

Enantiomers have same physical properties but may be distinguished from each other by the ability
they rotate polarized light due to optical activity.
If the rotation of the plane is in clockwise direction (to the right), the substance is dextrorotatory
(with + sign) while if the rotation is in the anticlockwise (to the left), the substance is laevorotatory
(with – sign). The degree of rotation is determined by use of a polarimeter.
CONFORMATION
A conformation of an acyclic molecule is a specific disposition/ arrangement of atoms in the
molecule in space within the molecule due to free rotation around sigma bonds.

e.g.: ethane (CH3CH3)

Due to free rotation around the carbon-carbon bond, the ethane molecule could assume an infinite
number of conformations, two of which are shown below as saw-horse formulae.

Saw- horse projection of ethane

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In the eclipsed conformation of ethane, the smallest dihedral angle is 0º, whereas in the staggered
conformation it is 60º, which can be seen more clearly in the respective Newman projection.

Newman projection of ethane

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IDENTIFICATION AND STRUCTURAL DETERMINATION OF ORGANIC
COMPOUNDS

Separation and Purification of Organic Compounds

There are so many methods used to separate and purify mixture of organic compounds as discussed
below:

▪ Chromatography

Chromatography is the separation of a mixture by passing it in solution or suspension or as a

vapor (as in gas chromatography) through a medium in which the components move at different
rates. Thin-layer chromatography is a special type of chromatography used for separating and
identifying mixtures that are or can be colored, especially pigments. Examples of chromatographic
techniques include:

- Gas chromatography. Gas chromatography (GC) is an analytical technique used to separate

the chemical components of a sample mixture and then detect them to determine their
presence or absence and/or how much is present. These chemical components are usually
organic molecules or gases. For GC to be successful in their analysis, these components
need to be volatile, usually with a molecular weight below 1250 Da, and thermally stable
so they don’t degrade in the GC system. GC is a widely used technique across most
industries: for quality control in the manufacture of many products from cars to chemicals
to pharmaceuticals; for research purposes from the analysis of meteorites to natural
products; and for safety from environmental to food to forensics. Gas chromatographs are
frequently hyphenated to mass spectrometers (GC-MS) to enable the identification of the
chemical components.

- High Performance Liquid chromatography. High Performance Liquid Chromatography

(HPLC) is a form of column chromatography that pumps a sample mixture or analytes in
a solvent (known as the mobile phase) at high pressure through a column with
chromatographic packing material (stationary phase). The sample is carried by a moving
carrier gas stream of helium or nitrogen. HPLC has the ability to separate, and identify
compounds that are present in any sample that can be dissolved in a liquid in trace
concentrations as low as parts per trillion. Because of this versatility, HPLC is used in a
variety of industrial and scientific applications, such as pharmaceutical, environmental,
forensics, and chemicals.

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 Sample retention time will vary depending on the interaction between the stationary phase,
the molecules being analyzed, and the solvent, or solvents used. As the sample passes
through the column, it interacts between the two phases at different rate, primarily due to
different polarities in the analytes. Analytes that have the least amount of interaction with
the stationary phase or the most amount of interaction with the mobile phase will exit the
column faster.
- Thin Layer Chromatography. Thin layer chromatography is a kind of chromatography used
to separate and isolate mixtures that are non-volatile in nature. Just like other chromatography
processes, this one consists of a mobile phase and a stationary phase. The latter one here is a
thin layer of absorbent material, such as aluminum oxide, silica gel, or cellulose. This layer is
applied to plastic, glass, or aluminum foil sheets called an inert substrate. The mobile phase in
the TLC procedure is a solvent or a mixture of it.

The separation principle of the TLC procedure is based on the given compound’s relative
affinity towards the mobile and the stationary phase. The process begins here by moving the
mobile phase over the stationary phase’s surface. During this movement, the higher affinity
compounds gain less speed as compared to the lower affinity compounds. This results in their
separation. Once the procedure gets completed, different spots can be found on the stationary
surface at distinct levels, reflecting various elements of the mixture. Basically, the compounds
that are more attracted towards the stationary phase secure their position at lower levels while
others move towards the higher levels of the surface. So their spots can be seen accordingly.

- Column chromatography. Column chromatography is described as the useful technique in

which the substances to be isolated are presented onto the highest point of a column loaded
with an adsorbent (stationary phase), go through the column at various rates that rely upon the
affinity of every substance for the adsorbent and the solvent or solvent mixture, and are
typically gathered in solution as they pass from the column at various time. The two most
common examples of stationary phases for column chromatography are silica gel and alumina
while organic solvents are regarded as the most common mobile phases.

- The main principle involved in column chromatography is the adsorption of the solutes of the
solution with the help of a stationary phase and afterward separates the mixture into
independent components. At the point when the mobile phase together with the mixture that
requires to be isolated is brought in from the top of the column, the movement of the individual
components of the mixture is at various rates. The components with lower adsorption and
affinity to the stationary phase head out quicker when contrasted with the greater adsorption
and affinity with the stationary phase. The components that move rapidly are taken out first
through the components that move slowly are eluted out last.

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 The adsorption of solute molecules to the column happens reversibly. The pace of the
movement of the components is communicated as: Rf = the distance traveled by solute/ the
distance traveled by the solvent, where Rf is called retardation factor.

- Flush column chromatography. Flash column chromatography was developed in 1978 as

an alternative method to long column chromatography. The method aims to isolate a
component from a mixture and thereby purify it. It was built from existing long column
chromatography technology, which was time-consuming and often not satisfactory. Flash
column chromatography, in short, passes a sample through a column filled with a gel,
which separates the sample, under applied external pressure to move the mobile phase
faster down the column as fractions are collected and monitored using TLC plates.

▪ Distillation

Distillation is an effective method to separate mixtures comprised of two or more pure liquids.
Distillation is a purification process where the components of a liquid mixture are vaporized and
then condensed and isolated.

In simple distillation, a mixture is heated and the most volatile component vaporizes at the lowest
temperature. The vapor passes through a cooled tube (a condenser), where it condenses back into
its liquid state. The condensate that is collected is called distillate.

Fractional distillation is a process by which components in a chemical mixture are separated into
different parts (called fractions) according to their different boiling points. Fractional distillation
is used to purify chemicals and to separate mixtures to obtain their components.

▪ Evaporation

Evaporation is a technique used to separate out homogenous mixtures where there is one or more
dissolved solids. This method drives off the liquid components from the solid components. The
process typically involves heating the mixture until no more liquid remains. Prior to using this
method, the mixture should only contain one liquid component, unless it is not important to isolate
the liquid components. This is because all liquid components will evaporate over time. This
method is suitable to separate a soluble solid from a liquid.

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 ▪ Filtration

Filtration is a separation method used to separate out pure substances in mixtures comprised of
particles some of which are large enough in size to be captured with a porous material. Particle
size can vary considerably, given the type of mixture. For instance, stream water is a mixture that
contains naturally occurring biological organisms like bacteria, viruses, and protozoans. Some
water filters can filter out bacteria, the length of which is on the order of 1 micron. Other mixtures,
like soil, have relatively large particle sizes, which can be filtered through something like a coffee
filter.

▪ Crystallization

Common terms used in crystallization:

➢ Crystallization
Crystallization is a process whereby solid crystals are formed from another phase, typically
a liquid solution or melt.
➢ Crystal
Crystal is a solid particle in which the constituent molecules, atoms, or ions are arranged
in some fixed and rigid, repeating three-dimensional pattern or lattice.
➢ Precipitation
Precipitation is the process of generating solid from the solution caused by supersaturation
when the concentration of the solute is higher than its solubility. This term is usually
interchangeable with "crystallization", but differs in that it can also indicate the formation
of amorphous (non-crystalline) solid.
➢ Solubility
Solubility is a measure of the amount of solute that can be dissolved in a given solvent at
a given temperature
➢ Saturated Solution
At a given temperature, there is a maximum amount of solute that can be dissolved in the
solvent. At this point the solution is saturated. The quantity of solute dissolved at this point
is the solubility.

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 ➢ Supersaturation
Supersaturation can mean the status that the actual solute concentration is higher than the
equilibrium solute concentration (solubility), or the degree of how much the concentration
is higher than the solubility.

Crystallization, or crystallisation, is the process of atoms or molecules arranging into a well-

defined, rigid crystal lattice in order to minimize their energetic state. The smallest entity of crystal
lattice is called a unit cell, which can accept atoms or molecules to grow a macroscopic crystal.
During crystallization, atoms and molecules bind together with well-defined angles to form a
characteristic crystal shape with smooth surfaces and facets. Although crystallization can occur in
nature, crystallization also has a broad industrial application as a separation and purification step
in the pharmaceutical and chemical industries.

Crystallization occurs when the solubility of a solute in solution is reduced by some means.
Common methods to reduce solubility include:

• Cooling
• Anti-solvent Addition
• Evaporation of Solvent
• Precipitation Through Chemical Reaction

The choice of crystallization method depends on the equipment available for crystallization, the
objectives of the crystallization process and the solubility and stability of the solute in the chosen
solvent.

Crystallization Steps

i. Choose an appropriate solvent. Common considerations included how much solute can be
dissolved (solubility) and how practical the solvent is to handle (safety)
ii. Dissolve the product in the solvent by increasing the temperature until all solids of the
product are dissolved. At this moment, insoluble impurities may be filtered from the hot
solution

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 iii. Reduce solubility via cooling, anti-solvent addition, evaporation or reaction. The solution
will become supersaturated.
iv. Crystallize the product. As solubility is reduced, a point is reached where crystals will
nucleate and then grow. Highly pure product crystals should form and impurities should
remain in solution.
v. Allow the system to reach equilibrium to maximize the yield of product solid.
vi. Filter and dry the purified product.

▪ Recrystallization

Recrystallization is a technique used to purify solid compounds. Solids tend to be more soluble in
hot liquids than in cold liquids. During recrystallization, an impure solid compound is dissolved
in a hot liquid until the solution is saturated, and then the liquid is allowed to cool. The compound
should then form relatively pure crystals. Ideally, any impurities that are present will remain in the
solution and will not be incorporated into the growing crystals. The crystals can then be removed
from the solution by filtration. Not all of the compound is recoverable — some will remain in the
solution and will be lost.

Recrystallization is not generally thought of as a separation technique; rather, it is a purification

technique in which a small amount of an impurity is removed from a compound. However, if the
solubility properties of two compounds are sufficiently different, recrystallization can be used to
separate them, even if they are present in nearly equal amounts. Recrystallization works best when
most impurities have already been removed by another method, such as extraction or column
chromatography.

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DETERMINATION OF MOLECULAR FORMULA

Methods of Relative Molecular Mass Determination of Organic Compounds

The four commonly used methods for determining the relative molar mass of organic compounds
include:
(a) Vapour density measurements using gas syringe or Victor Meyer’s method
Example
A hydrocarbon Q contains 91.3% carbon and the rest hydrogen.
(a) Determine the empirical formula of Q (C=12, H=1)
(b) The vapour density of Q is 39 at a constant temperature and pressure.
Determine the:
(i) Molecular mass of Q
(ii) Molecular formula of Q
(c) Q burns with a sooty flame, write down the possible isomer(s) of Q
Solution:
(a) Elements: C H
Masses (%): 91.3 8.7
91.3 8 .7
Moles:
12 1
= 7.6083 8.7
7.6083 8.7
Mole ratio: :
7.6083 7.6083
= 1 : 1
 E.F. of Q is CH
M .mass
(b) (i) From = v.density M .mass = 39  2 = 78 g
2
(ii) From M.F= (E.F) n = M .mass

(CH ) n = 78 Or n (12+1) = 78n = 6

 M .F Of Q is C6H6

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By Mr. Kumakech Colline
(c) The molecular structure of Q is

Example
When 0.29g of substance Q was burnt in oxygen, 0.66g of carbon dioxide and 0.27g of water were
formed.
(a) Calculate the empirical formula of Q
(b) Q forms a yellow solid with 2, 4-dintrophenylhydrazine. The vapour density of Q is 29.
(i) Write the structural formulae of the isomers and names of Q
(ii) What type of structural isomerism is exhibited by Q.?
(iii) How can the structural isomers be differentiated
Solution:
(a) RFM of CO2 = 1(12) + 2(16) = 44 Elements: C H O
RFM of H2O = 2(1) + 1 (16) = 18 Masses (g): 0.18 0.03 0.08
1(12) 0.18 0.03
Mass of Carbon in Q =  0.66 = 0.18g moles:
44 12 1
0.08
= 0.015
16
0.03 0.005
2(1) 0.015 0.03 0.005
Mass of Hydrogen in Q =  0.27 = 0.03g Ratio:
18 0.005 0.005 0.005
 Mass of Oxygen in Q = 0.29- (0.18+ 0.03) 3: 6 : 1

= 0.08g  E.F. of Q is C3 H6 O

(b) (i) M. mass of Q = 29×2 = 58g  (C3H6O) n = 58

 n (3(12) +6(1) + 1 (16)) = 58 or 58n = 58 or n= 1

M.F of Q is C3H6O with S.F CH3COCH3 –Propanone and CH3CH2CHO- Propanal

(ii) Functional Isomerism

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By Mr. Kumakech Colline
 (iii) By using Ammoniacal Silver nitrate solution
Example
(a) Define the hydrocarbon
(b) A compound X, on combustion gave 0.629g of carbon dioxide and 0.257g of water.
Determine the empirical formula of X
(c) When 0.10g of X was vapourised, it occupied a volume of 40cm3 at s.t.p
(i) Calculate the molecular mass of X
(ii) Determine the molecular mass of X hence write the structural formulae of the possible
isomers

Solution:
(a) A compound that contains carbon and hydrogen as the only elements present
1(12)
(b) Mass of Carbon =  0.629 = 0.1715g (ii) (CH2) n = 56
44
2(1)
Mass of Hydrogen =  0.257 = 0.0286 g n (12+2) = 56  n = 4
18
Elements: C H  M.F of X is C4H8

0.1715 0.0286
Moles:
12 1
CH3C CH2
CH3
= 0.0143 0.0286

Hence mole ratio = 1:2  E.F of X is CH2 CH3CH2CH CH2

mRT CH3CH CHCH3

(c) (i) From PV = nRT  Mr =
PV
0.1  8.314  273
= = 56 g
101325  40  10 −6

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By Mr. Kumakech Colline
(b) Colligative Properties of dilute solutions containing non-volatile solutes
These include lowering of vapour pressure, cryoscopy, ebullioscopy and osmotic pressure.
Cryoscopic method has an advantage over ebullioscopic method that it is not affected very much
by pressure changes of which boiling points depend on the atmospheric pressure.
Molecular mass of polymers is determined using Osmotic pressure because they are easily
denatured by heat and presence of polymer changes the osmotic pressure of the solvent
significantly.
Example
A compound W contains Carbon, Hydrogen and oxygen. When 1.5g of W was burnt in excess
oxygen, 1.467g of carbon dioxide and 0.297g of water were formed.
(a) Determine the empirical formula of W
(b) 7.5g of W was dissolved in 204.4g of water to a solution. The prepared boiled at 100.212oC.
The boiling point constant of water is 0.52oC per mole per kg.
Determine the:
(i) Molecular mass of W
(ii) Molecular formula
(iii) Structural formula of w
(c) State the condition(s) employed in order for W to react with following compounds.
In each case write the equation of reaction
(i) Sulphuric acid
(ii) Potassium manganate (VII) solution
(d) Name the reagent that can be used to distinguish between W and Methanoic acid.
Solution:
2 12
(a) Mass of hydrogen =  0.297 = 0.033g, Mass of Carbon =  1.467 = 0.40 g
18 44
 Mass of oxygen = 1.5- (0.033+0.40) = 1.067g

Elements: C H O 0.033 0.033 0.067

0.40 0.033 1.067
Moles:  Mole ratio: 1: 1: 2
12 1 16

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By Mr. Kumakech Colline
  E.F of W is CHO2

T = 100.212 − 100 = 0.212 o C

(b) (i) 204.4g of water contains 7.5g of W

7.5
 1000g of water contains  1000 = 36.69 g of W.
204.4
0.212oC is the elevation in b.p.t caused by 36.69g of W
36.69
 0.52 oC is the elevation in b.p.t caused by  0.52 = 90 g of W
0.212
90
(ii) (CHO2)n= 90  n = = 2  M.F of W is C2H2O4
45
COOH

(iii) COOH

(c) (i) Concentrated acid and heat

Conc.H2SO4
H2C2O4 H2O + CO + CO2
Heat

(ii) Acidified Potassium permanganate solution and warm the solution to about 70oC
5C2O42- (aq) + 2MnO4- (aq) + 16H+ (aq) 10CO2 (g) + 2Mn2+ (aq) + 8 H2O (l)

(d) Ammoniacal Silver nitrate solution

Example
(a) Differentiate between Diffusion and Osmosis
(b) The osmotic pressure of a solution containing 4.00gdm-3 of polyvinylchloride,

CH2=C H

Cl n

In dioxin is 65Pa at 20oC. Determine the number of monomers, n, in the polymer.

(c) State two conditions under which the Osmotic laws cannot be obeyed

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By Mr. Kumakech Colline
Solution
(a) Diffusion is the movement of molecules from high concentrated area to a low concentrated
area while Osmosis is the movement of solvent molecules from a dilute solution to
concentrated solution across a semi-permeable membrane
mRT 4  8.314  293
(b) From v = nRT  Mr = = −3
= 149.91  10 3
V 65  10
 n (24+3 + 35.5) =149.91X103  n = 2399

(c) When the solution is concentrated

When the solute associate or dissociate in the solvent
(c) Eudiometry method or Gaseous explosion
This method is suitable for gaseous hydrocarbon only
Example
(a) State Gay-Lussac’s law.
(b) 30cm3 of a gaseous hydrocarbon Y burnt at constant temperature and pressure produced
120cm3 of carbon dioxide and 120cm3 of steam.
(i) Determine the formula of Y.
(ii) Write structures and names of all the isomers of Y.
Solution
(a) When gases combine together at a constant temperature and pressure they do so in volumes
which bear a simple ratio to each other and to the volume of gaseous product.
(b) (i)

CxHy + (x+y/4) O2 xCO2 + y/2H2O

30cm3 30(x+y/4)cm3 30xcm3 15ycm3

15y=120 or y= 8
30x=120 or x=4 C4H8

(ii)

CH3CH2CH CH2 CH3CH CHCH3 CH3C CH2

CH3

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By Mr. Kumakech Colline
Example
30cm3 of gaseous hydrocarbon were mixed with 140cm3 of excess oxygen and exploded. After
cooling to room temperature, the residual gases occupied 95cm3. By absorption with potassium
hydroxide solution a diminution of 60cm3 was produced. Determine the molecular mass of the
hydrocarbon
Solution
Cx Hy + (x+ y/4) O2 xCO2 + y/2 H2O
3ocm3 30(x + y/4) cm3 30xcm3 15ycm3
 Volume of excess oxygen = 95-60 = 35cm3
Volume of Oxygen used = 140-35= 105cm3
Also, Volume of carbon dioxide produced= 60cm3
60 y 105
 30x=60 or x= = 2 Also ( x + ) = = 3.5 or y=6
30 4 30
M.F of the hydrocarbon is C2H6 with molecular mass = 2(12) + 6(1) = 30g
(d) Steam Distillation
This is the technique of separating a volatile substance that is immiscible with water from a
non-volatile component at a temperature below its boiling point.
This method helps in separating organic compounds that decompose near their boiling point
and distil at a temperature below their boiling points.
It uses the principle of
n1 p
= 1 Where n1 and n2 are moles of component 1 and 2 respectively with vapour
n2 p 2
pressure P1 and P2 respectively
m1 W1 p1
 = Where W1 and W2 are the molecular mass of 1 and 2 respectively
m2 W2 p 2

Example
(a) When 4.9g of an organic compound X was burnt in excess oxygen, 14.78g of carbon dioxide
and 5.38g of steam was formed. Calculate the simplest formula of X
(b) X was steam distilled at 80oC and 760mmHg and the distillate was found to contain 90.8%
by mass of X. The vapour pressure of water at the same temperature is 240mmHg.
(i) Calculate the formula mass of X

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By Mr. Kumakech Colline
 (ii) Deduce the molecular formula of X
(iii) Write down the possible isomers of X
12
Solution: Mass of Carbon =  14.78 = 4.304 g
44
2
Mass of Hydrogen=  5.38 = 0.598 g
18
Elements: C H
4.304 0.598
Moles:
12 1
Ratio 1 : 1.667
 3 : 5 hence E.F. of X is C3H5

m1 W1 p1
(b) (i) From =  PT =P1+ P2 or P2= 760-240 = 520mmHg and m1
m2 W2 p 2
= 100 - 90.8 = 9.2
9.2 18  240
= W2 = 81.99 g
90.8 W2  520

82
(ii) (C3H5) n = 82 or n = = 2  M.F of X is C6H10
41

(iii) The isomers are

CH3CH2CH2CH2C CH CH3CH2CH2C CCH3 CH3CH2C CCH2CH3

CH3
CH3CHC CCH3 CH2 CHCH2CH2CH CH2
CH3CC CH

CH3
CH3

CH3

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By Mr. Kumakech Colline
SPECTROSCOPY AND STRUCTURAL DETERMINATION OF ORGANIC
COMPOUNDS

Spectroscopy is the study of the absorption and emission of light and other radiation by matter. It
involves the splitting of light (or more precisely electromagnetic radiation) into its constituent
wavelengths (a spectrum), which is done in much the same way as a prism splits light into a
rainbow of colors. In fact, old style spectroscopy was carried out using a prism and photographic
plates.

Modern spectroscopy uses diffraction grating to disperse light, which is then projected onto CCDs
(charge-coupled devices), similar to those used in digital cameras. The 2D spectra are easily
extracted from this digital format and manipulated to produce 1D spectra that contain an
impressive amount of useful data.

Recently, the definition of spectroscopy has been expanded to also include the study of the
interactions between particles such as electrons, protons, and ions, as well as their interaction with
other particles as a function of their collision energy.

Spectroscopy and Spectrometry used in Organic Chemistry

Spectroscopy is the science of studying the interaction between matter and radiated energy. It’s
the study of absorption characteristics of matter, or absorption behaviour of matter, when subjected
to electromagnetic radiation. Spectroscopy doesn’t generate any results, it’s simply the theoretical
approach to science.

On the other hand, spectrometry is the method used to acquire a quantitative measurement of the
spectrum. It’s the practical application where results are generated, helping in the quantification
of, for example, absorbance, optical density or transmittance.

In short, spectroscopy is the theoretical science, and spectrometry is the practical measurement in
the balancing of matter in atomic and molecular levels.

Spectroscopic techniques

i. UV- Vis Spectroscopy: UV-VIS spectrometer is used to determine the presence of

chromophores including conjugation within a molecule. The cut off wavelength of the
solvent is adjusted accordingly and a higher value of λmax from absorbance spectrum
shows presence of more conjugation within the molecule.

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By Mr. Kumakech Colline
 ii. Infrared spectroscopy: Infrared Spectrophotometer is used to determine the different
functional groups within the molecule. The different functional groups have different
absorbance at different wavelength (wave number).

iii. Mass spectroscopy: This is used to determine the molecular weight of the different
compounds, and possibly that of the fragments. The compounds are subjected to Mass
spectrophotometer and their molecular masses can be read from the mass spectra
produced.

iv. NMR spectroscopy: This is used to identify protons and carbon atoms within the
molecule. It has both 1D and 2D, which yield information used to identify carbon and
protons present in a compound.

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By Mr. Kumakech Colline