MODUL 1

ORGANIC CHEMISTRY

CHAPTER 1
CHEMISTRY OF CARBONS

1
 TOPIC 1.1 BONDING OF THE CARBON ATOMS: THE SHAPES OF
THE ETHANE, ETHENE, ETHYNE, AND BENZENE
MOLECULES

LEARNING OBJECTIVES:
1. To explain the concept of hybridisation in the bonding of carbon atoms with reference
specially to carbon atoms which have a valency of four and the types of hybridisation such
as the following:
sp − linear, sp2 − triangular, sp3 − tetrahedral

2. To describe the formation of σ and π bonds as exemplified by diagrams of the overlapping

of orbitals in CH4, C2H4, C2H2, and C6H6 molecules

3. To explain the concept of delocalisation of π electrons in benzene rings (aromaticity)

Hybridisation of 2s and 2p orbitals in carbon atoms:

 Each carbon atom has valence electrons  Valency of carbon atom is

 Carbon could undergo 3 types of orbital hybridisation before it forms covalent bonds with

another atom:

 Energy level diagrams to show the sp3, sp2 and sp hybridisation in carbon atom:

Carbon atom (ground state)

Carbon atom (excited state)
Carbon atom (sp3 hybridised)
sp3 orbitals are formed
The number of sp3 orbitals formed:
Energy of all sp3 orbitals:
2p 2p Shape:
Bond angle: e.g:
sp3
Energy

Energy

Energy

2s 2s

1s 1s 1s
 Carbon atom (excited state)Carbon atom (sp2 hybridised)
Carbon atom (ground state)
2p sp2 orbitals are formed
2p 2p
energy

sp2

Energy
Energy

Energy
2s 2s

Shape: Bond angle: e.g:

1s 1s 1s

Carbon atom (ground state)

Carbon atom (excited state)Carbon atom (sp hybridised)
2p 2p 2p sp orbitals are formed
energy

sp
Energy

Energy

Energy

2s 2s

Shape: Bond angle: e.g:

1s 1s 1s

The Formation of σ and π Bonds

Two Types Of Covalent Bonds sigma (σ) bond

Formed (In Term Of Orbital
Overlapping)
pi (π) bond
• sigma (σ) bond

 orbitals overlapping :

• pi (π) bond
 orbitals overlapping :

Tutorial:
Based on how the following orbitals overlap, classify the following bonds as sigma (σ) bond
and pi (π) bond.
CH4:
Structural formula Molecular Shape
H Orbital hybridisation of Ca:
H Ca
Shape:
HH
Orbital overlapping diagram: H-C-H bond angle:

The total number of σ bond:

The total number of π bond:

C2H4:
Structural formula Molecular Shape
H H Orbital hybridisation of Ca:
H Ca Cb H
Orbital hybridisation of Cb:
Orbital overlapping diagram:
H–Ca–H bond angle:

H–Cb–H bond angle:

The total number of σ bond:

The total number of π bond:

C2H2:
Structural formula Molecular Shape
H Ca Cb H Orbital hybridisation of Ca:
Orbital hybridisation of Cb:
Orbital overlapping diagram:
H–Ca– Cb bond angle:
The total number of σ bond:
The total number of π bond:
C6H6 :
Structural formula Molecular Shape Orbital hybridisation of Ca,Cb,Cc,Cd,Ce & Cf:
H H
Ca Cb
H Cf Cc H H–Ca–Cb bond angle:
Ce Cd
H H Ca–Cb–H bond angle:
Orbital overlapping diagram:
H–Cd–Ce bond angle:

Ca–Cb–Cc bond angle:

Cd–Ce–Cf bond angle:

The total number of σ bond:

The total number of π bond:

TOPIC 1.2 GENERAL, EMPIRICAL, MOLECULAR, AND

STRUCTURAL FORMULAE FOR ORGANIC CHEMISTRY

LEARNING OBJECTIVES:
1. To explain the meaning of general, empirical, molecular, and structural formulae of
organic compounds
2. To calculate empirical formulae and derive molecular formulae

Define:
 General formula
 Shows the molecular formula of a class of compounds, in which the number of atoms
in the molecule is presented by x, y, n, etc.
 Empirical formula
 Shows the of the atoms present in the molecule.
 Molecular formula
 Shows the of each type of atom present in the molecule.
 Structural formula
 Shows the of each type of atom present in the molecule.
 Shows how the atoms are to each other.
 The structural formula can be represented in the form of:




Tutorial:
Molecular Empirical Condensed Structural Displayed/ Expanded
Skeletal formula
Formula Formula Formula Structural Formula

CH3CH2CH3

CH3(CH2)4CH3

CH3CH2CH2OH

CH3CHOHCH(CH3)2

CH3CH2CH2Cl

Cl

CH3CH=CH2

CH3CH=C(CH3)CH(CH3)2

CH3COOCH(CH3)2

CH3CH2OCH2CH3

OH

OH
H Cl O
CH3 C OH
C
H
C
CH3
H H H
CH3 C C C NH2
H CH3H
 To determine the empirical formula of a compound, X

Element C O H

Mass/ g 1.00 1.33 0.25

Relative atomic
mass, Ar

Number of moles
=
Lowest Mole ratio

Hence, the empirical formula of organic compound X =

Given: Relative molecular mass = 62
Let the molecular formula of organic compound X = ( )n

n = = =

Therefore, the molecular formula of organic compound X =

SUMMARY:
Definitions of Molecular Formula, Empirical Formula & Structural Formula
Molecular formula Empirical formula Structural formula
The type of atoms in the molecule
The number of each atom in the
molecule
The bonding between atoms in the
molecule

TOPIC 1.3 ISOMERISM: STRUCTURAL, GEOMETRIC, AND OPTICAL

LEARNING OBJECTIVES:
1. To interpret structural isomerism with reference to the ability of carbon atoms to link
together with each other in a straight line and/or in branches
2. To explain geometric/cis-trans isomerism in alkenes in terms of restricted rotation due to
π bond/ C=C bonds
3. To explain the meaning of a chiral centre and how such a centre gives rise to
optical isomerism
4. To identify chiral centres and/or cis-trans isomerism in a molecule of given
structural formula
5. To determine the possible isomers for an organic compound of known molecular formula
DEFINE:
ISOMERISM :

ISOMERS :

TWO MAIN TYPES OF ISOMERISM

Positional
1. Structural isomerism Chain
Functional group

cis
Geometrical isomerism trans
2. Stereoisomerism
Mirror images (non-
Optical isomerism
superimposable)

COMPARISON OF STRUCTURAL ISOMERISM AND STEREOISOMERISM:

Structural
Type of isomers Molecular formulae Functional group
formulae
Structural isomers
Stereoisomers

STRUCTURAL ISOMERISM:
 Occurs when atoms are
 Occurs in compounds having the same but
different .
 Three types of structural isomerism:

 Chain isomerism: Occurs when there are different arrangements of the
 Positional isomerism: Occurs when the same is placed at different

 Functional group isomerism: Occurs when there are different

 Chain isomerism:
 Example: C5H12

Pentane 2-methylbutane 2,2 – dimethylpropane

 Example: C4H10
 Positional isomerism:
 Example: C4H8  Example: C6H4Cl2

But-1-ene But-2-ene
 Example: C3H7OH

 Functional group isomerism:

 Example: C2H6O

Ethanol (an alcohol) dimethyl ether (an ether)

Different functional groups

COMPARISON OF STRUCTURAL ISOMERISM:

Type of structural Molecular Structural Carbon Functional Position of
isomers formulae formulae chain group Functional group
Chain isomers
Positional isomers
Functional group isomers

STEREOISOMERISM
 Occurs when compounds with same
has different .
 Two types of stereoisomerism:



GEOMETRICAL ISOMERISM
 Meaning: Isomerism that occurs/ arises when

 Two conditions:


 Example:
 But-2-ene: H CH3 H H
C C C C
H3C H H3C CH3
trans-but-2-ene cis-but-2-ene

 1,2-diiodocyclohexane: H H H I

I I I H
cis-1,2-diiodocyclohexane trans-1,2-diiodocyclohexane
  CHCl=CHCl:

OPTICAL ISOMERISM
 Occurs in compounds with the same molecular formula and Important Terminology:
structural formula that …  Plane polarised light:
 Do not have a plane of symmetry.
 Have a chiral centre/ chiral carbon (this C* is attached to four
different atoms/ groups)
a
 i.e: y C*  Chiral carbon:

bx
 The pair of optical isomers is called ,
 they are of one another, and
 are .  Enantiomers:

 Two conditions for optical activity:




 Example:
 2-chloro-2-butanol:  CH3CHClBr:
CH3 CH3
C C
C 2 H5 C2H5
Cl Cl
O HO
 CharacteristicHof enantiomers:
 Enantiomers are optically , ie: is able to
.
 Are superimposable.
 Enantiomers have physical properties (except for )
and chemical properties.
 Can be separated by a method called resolution.
 Two types of enantiomers based on their optical activity (how they rotate plane-polarised light):
Initial After passing through optical isomer

(+)-isomer/ dextrorotary isomer/

D–isomer

(–)-isomer/ laevorotary isomer/

Plane-polarised L–isomer
light

10
  How to remember the L–isomer and D–isomer?

D L
 A racemate/ racemic mixture: Important Terminology:
 Racemate:
 Contains quantities of L–
isomer and D–isomer.
 Since the amounts of L–isomer and D–isomer are the same,
the two isomers cancel out each others light polarising effect.
Hence, a racemate
plane-polarised light.

TUTORIAL:
1. Draw all the structural formulae and give the IUPAC name of the isomers for a compound with
a molecular formula of
a. C3H7OH: [2] b. C3H4Cl2: [7]

2. Draw and name all the stereoisomers for compound Y with a molecular formula of CH3CH=CHCl.

SUMMARY: ISOMERISM

Molecular Structura Spatial Chemical Chemica Optical

Types of Isomers m.p. & b.p.
formulae l arrangement propertie l activity
formulae s reactivit
y

Chain isomers

Structural Positional
isomers isomers
Functional
group isomers
:
-
Stereo- :
isomers D:
Enantiomers
L:
TOPIC 1.4 CLASSIFICATION BASED ON FUNCTIONAL GROUPS
(GENERAL FORMULA)
TOPIC 1.5 NOMENCLATURE AND STRUCTURAL FORMULAE FOR
EACH FUNCTIONAL/RADICAL GROUP (REFER TO THEIR
TRIVIAL NAMES)

LEARNING OBJECTIVES:
1. To describe the classification of organic compounds by functional groups and the
nomenclature of classes of organic compounds according to the IUPAC system of
the following classes of compounds:
a. alkanes, alkenes
b. haloalkanes
c. alcohols (including primary, secondary and tertiary) and phenols
d. aldehydes and ketones
e. carboxylic acids and esters
f. primary amines, amides, and amino acids

Homologous Functional group

General formula Structural formula Nomenclature
series

1 Alkane

2 Alkene

3 Haloalkane

4 Alcohol

5 Phenol

6 Aldehyde

7 Ketone

8 Carboxylic acid

9 Ester

10 Primary amine

11 Amide

12 Amino acid
 NOMENCLATURE:

Prefix Suffix

Indicates the number of carbon atoms in the longest continuous

Represents
chain. the homologous series of the compound.

Number of Number of Homologous

Prefix Prefix Suffix
C atoms C atoms series
1 Meth- 11 Undec-
Alkane -ane
2 Eth- 12 Dedec-
Alkene -ene
3 Prop- 13 Tridec-
Haloalkane Halo- -ane
4 But- 14 Tetradec-
5 Pent- 15 Pentadec-
Alcohol -ol
6 Hex- 16 Hexadec- Aldehyde -al
7 Hept- 17 Heptadec- Ketone -one
8 Oct- 18 Octadec- Carboxylic acid -anoic acid
9 Non- 19 Nonadec- Primary amine -anamine
10 Dec- 20 Eicos- Amide -anamide

IUPAC Nomenclature of organic compounds:

1. Find the longest chain of carbons in the molecule. The number of carbons in the longest
chain becomes the parent name (refer to the above table)
2. After finding the parent chain, you number the parent chain starting with the end nearest to
the first substituent (a substituent is any fragment that juts off the main chain).
3. Next, determine the names of all substituents. Substituents are named as if the piece were a
separate molecule, except that the suffix of -yl is used rather than -ane. E.g.:
Alkyl, R methyl ethyl propyl isopropyl butyl
Structural –C2H5 / CH3
–CH3 –CH2CH2CH3 –CH2CH2CH2CH3
formula –CH2CH3 CHCH3

Alkyl, R isobutyl phenyl benzyl

Structural CH3 –C6H5 C6H5CH2–
formula CH2CHCH3
CH2
–CH2CH (CH3)2 Or

4. Put the substituents in alphabetical order (ie. ethyl before methyl) in front of the parent name.
5. Next, identify the positions of all substituents in the name by placing the carbon number where
the substituent attaches to the parent chain in front of it. For identical substituents, use the prefix
di-, tri- or tetra-.
6. Separate numbers using commas.
7. Separate numbers from letters by hyphens.
TUTORIAL:
For each of the following molecules, identify its homologous series and name the compound.

(a) C6H5CH2 = CH2 (g) HCOOCH2CH3

(b) CH2CH2CH(OH)CH3 (h) CH3COOC6H5
(c) C6H5CH2OH (i) CH3CH2CH2NH2
(d) C6H5OH (j) CH3CH(NH2)CH2CH3
(e) C6H5COOH (k) CH3CH2CH2Br
(f) CH3CH2COOH (l) CH3CH2CH2CONH2

TOPIC 1.6 NUCLEOPHILE AND ELECTROPHILE

LEARNING OBJECTIVES:
1. To define the terms nucleophile and electrophile
2. To explain the meaning of Lewis acids and bases in terms of charge/electron density
3. To explain why many organic compounds containing oxygen/nitrogen which have lone pair
electrons (as Lewis bases) form bonds with electron acceptors (as Lewis acids)
4. To explain how nucleophiles such as OH−, NH3, H2O, Br−, I− and carbonion have Lewis base
properties, whereas electrophiles such as H+, NO2+, Br2, AlCl3, ZnCl2, FeBr3, BF3, and
carbonium ions have Lewis acid properties

TUTORIAL: Define:
Classify each of the following species as electrophile  Nucleophile :
or nucleophile and explain your choice.
(a) CN– (i) OH− (q) ZnCl2
(b) H2O (j) NH3 (r) BF3  Electrophile :

(c) AlCl3 (k) I− (s) CH3CH2NH−

(d) Br− (l) FeCl3 (t) FeBr3  Lewis acid :
+
(e) H+ (m)CH3CH2 (u) HSO4−
(f) CH2=CH2 (n) CH3CH2NH2 (v) HSO3+
 Lewis base :
(g) NO2+ (o) Br2 (w) P(CH3) 3
(h) HCl (p) CH3COO− (x) CH3CH2O−
Comparison:
Species Nucleophile, ̈ Electrophile, E+
Electron density
Charge (for ionic species)
Presence of lone e– pairs
Electron acceptor/ donor
Lewis acid/ base
Oxidising/ Reducing Property
Reaction between nucleophile (Lewis base) and electrophile (Lewis acid):
Identify the following reactants as electrophiles or nucleophiles.
1. CH3Cl + OH–  CH3OH + Cl–

2. CH3CHO + Cl–  CH3CHClO–

3. FeCl3 + Cl2  FeCl – +4 Cl+

4. CH2=CH2 + Br2  CH2BrCH2Br

5. CH3CH2NH2 + HCl  CH3CH2NH3+ + Cl–

Classification of free radicals, electrophiles and nucleophiles:

 Free radicals:
H H H R
H C R C R C R C
H H R R

 Electrophiles:
H H H R
H C R C R C R C
H H R R

 Nucleophiles:

Stability of free radicals, electrophiles Important facts:

and nucleophiles: FR, E+ or ̈ appears as intermediate in rxn mechanisms.
 –R : Electron donating group  If the intermediate is stable, the reaction occurs

 Free radicals: CH3• 1° 2° 3°

 If the intermediate is unstable, the reaction occurs
 Electrophiles: CH3+
1° 2° 3°
 Species with higher charge density stable
 Nucleophiles: CH3– 1° 2° 3°  Species with lower charge density stable

EA: Alkene + Br2/ H2O/ HX
NA: Aldehyde/ ketone + HX
6 Common Organic Reactions:
FRS: Alkane + Halogen
Organic reactions Dehydration (–H2O): ROH
ES: Benzene + NO +/ 2Cl+/ Br+/ HSO +/ R
3
+

Dehydrohalogenation (–HX): RX
NS: ROH / RX + Nu–
Addition Substitution Elimination

INDUCTIVE EFFECT ON THE CHEMICAL PROPERTIES AND REACTIONS OF THE

FUNCTIONAL GROUP
Chemical Reaction
Homologous Functional
series group Succeptible to
Type of reaction Intermediate
attack of ...

1 Alkane

2 Alkene

3 Haloalkane

4 Alcohol

5 Aldehyde

6 Ketone

Carboxylic
7
acid

Primary
8
amine

TUTORIAL:
Classify each of the following organic reactions as elimination/ substitution/ addition:
(a) CH2=CH2 + H2  CH3–CH3
(b) CH3CH2CH3  CH3CH=CH2 + H2
(c) CH2=CH2 + Br2  CH2BrCH2Br
(d) CH3CH2CH3 + Br2  CH3CH2CH2Br + HBr
(e) CH2=CH2 + HOBr  CH2BrCH2OH
(f) CH3CH2Br + CN–  CH3CH2CN + Br –
(g) CH3OH + NH2–  CH3NH2 + OH–
(h) CH4 + Cl2  CH3Cl + HCl
(i) CH3CH2CN + 2H2  CH3CH2CH2NH2
(j) CH3COCl + NH2–  CH3CONH2 + Cl–
(k) CH3COCl + CH3O–  CH3COOCH3 + Cl–
(l) CH3CH2OH  CH2=CH2 + H2O

TOPIC 1.7 STRUCTURE AND ITS EFFECT ON

(A) Physical Properties; e.g. Boiling Point, Melting Point, And Solubility In Water
(B) Acidity And Basicity
The Effect Of The Structure And Delocalisation Of Electrons On The Relative Acid Or
Base Strength, i.e. Proton Donors Or Acceptors, In Ethylamine, Phenylamine, Ethanol,
Phenol, And Chlorine-Substituted Ethanoic Acids

LEARNING OBJECTIVES:
1. To describe the relationship between the size of molecules in the homologous series and the
melting and boiling points
2. To explain the attractive forces between molecules (van der Waals forces and hydrogen bonding)
3. To explain induction effect which can determine the properties and reactions of functional groups
4. To explain how most functional groups such as −NO2, −CN, −COOH, −COOR, >C=O, SO3H, −X
(halogen), −OH, −OR, −NH2, C6H5 are electron acceptors whereas functional groups such as −CH3,
−R (alkyl or aryl) are electron donors
5. To explain how the concept of induction can account for the differences in acidity between
CH3COOH, ClCH2COOH, Cl2CHCOOH, and Cl3CCOOH; between ClCH2CH2CH2COOH and
CH3CH2CHClCOOH
6. To use the concept of delocalisation of electrons to explain the differences in acidity between
ethanol and phenol, as well as the differences in basicity between CH 3NH2 and C6H5NH2

STRUCTURE AND ITS EFFECT ON BOILING POINT AND MELTING POINT:

POLAR MOLECULES (H2O,

ROH, RCOOH, NH3, RNH2)
• Hydrogen bonds
POLAR MOLECULES
• Van der Waals attractive forces
(permanent dipole - permanent
NON-POLAR MOLECULES dipole attractive forces)
• Van der Waals attractive forces
(induced dipole - induced dipole
attractive forces)
1. NON-POLAR MOLECULES:
 with different molecular mass:
 E.g.: CH4 < C3H8:
 Because:
 Molecular size:  Bigger molecule contains more .
 The strength of intermolecular attractive forces (Van der Waals):

 with approximately the same molecular mass/ molecular formula: 

 The shape of molecules that are extensively branched :
 The shape of linear molecules :
 E.g.: Boiling point
CH3CH2CH2CH2CH3 > CH3CH(CH3)CH2CH3 > CH3CH(CH3)2CH3 :
 Because:
 Degree of branching:
 Contact surface area between molecules:
 The strength of intermolecular attractive forces (Van der Waals):

 E.g.: Melting point

CH3CH2CH2CH2CH3 < CH3CH(CH3)CH2CH3 < CH3CH(CH3)2CH3 :
 Because:
 Degree of branching:
 Arrangement and packing in solid state:
(more compact) > > (less compact)
 The strength of intermolecular attractive forces (Van der Waals):

2. POLAR AND NON-POLAR MOLECULES:

 E.g.: C6H10 < C3H7Cl :
 Because:
 Type of intermolecular attractive forces in:
C6H10 :
C3H7Cl :
 The strength of i.m.f.: <

 E.g.: C4H10 < C3H7OH :

 Because:
 The intermolecular attractive forces in C4H10 is:
 The intermolecular attractive forces in C3H7OH is:
 The strength of intermolecular attractive forces:
(Van der Waals) < (Hydrogen bonds)
 E.g.: C5H12 < C4H9NH2 :
 Because:
 The intermolecular attractive forces in C5H12 is:
  The intermolecular attractive forces in C4H9NH2 is:
 The strength of intermolecular attractive forces:
(Van der Waals) < (Hydrogen bonds)
 Covalent molecules and ionic compounds:
 Ionic compound > Covalent molecules
 Because:
 More energy is required to break the strong in ionic compound
 Less energy is needed to overcome the weak
in covalent compound.

3. COMPOUNDS WITH INTERMOLECULAR HYDROGEN The strength of

intermolecular forces:
BONDS:
 H2O, NH3, CH3NH2 , CH3COOH, CH3OH > >
 Intermolecular forces:

TUTORIAL: Melting and boiling points

1. Different types of intermolecular forces exist in organic compounds.
a. Name these intermolecular forces.
b. Indicate the type(s) of intermolecular forces present in each of the compounds below.
(i) CH3CH2CH2CH2OH (ii) CH3CH2COOCH2CH3
(iii) CH3CH2CH2CH2CONH2 (iv) CH3CH2CH2CH2CHO
(v) CH3CH2CH2COOH (vi) CH3CH2CH2COCH3

(vii) CH3 (viii) COCl

(x) CH3CH2CH2NH2
(ix) Cl
(xi) CH3CH2CH2CH2CN (xii) CH3CH2OCH2CH3

2. Which of the following compounds have hydrogen bonding?

A (CH3)3N B CH3OH C CH3OCH3

D CHI3 E COOH

3. Arrange the following compounds in increasing order of boiling points.

CH3CH2CH2OH, CH3CH2CH2CH3, HOCH2CH2OH, CH3COCH3

4. The boiling points of isomeric pentane are shown below:

Isomer I II III
Boiling point / °C 36 28 10
Draw the structural formulae of the three isomers and explain the difference in their boiling
points.
5. Arrange the following compounds in decreasing order of volatility.
a. CH3CH2NHCH3, (CH3)3N, CH3CH2CH2NH2
b. (CH3)3COH, CH3CH2CH2CH2OH, CH3CHCH2CH3
OH
c. HCOOCH3, CH3COOH, CH3CH2CH2OH

6. What are the strongest attractive forces that must be overcome to:
a. boil CHCl3

b. vapourise

c. melt COOH

STRUCTURE AND ITS EFFECT ON SOLUBILITY IN WATER

1. COMPOUNDS WITH INTERMOLECULAR HYDROGEN BONDS (ALCOHOL,

CARBOXYLIC ACID, AMINE & AMIDE):

The ultimate rule: Like-Dissolves-Like

 H2O, NH3, CH3NH2 , CH3COOH, CH3OH, CH3CONH2

 Intermolecular attractive forces:
 These molecules are miscible with water. Because:
 E.g.: H2O and NH3 , H2O and CH3NH2, H2O and CH3COOH, H2O and CH3OH
 Condition: Total number of carbon atoms in the molecule must not exceed
 Because:

2. H2O & ORGANIC COMPOUNDS THAT ARE NOT MENTIONED ABOVE:

 Non-polar compounds: Alkane, alkene, benzene,
 Intermolecular forces in non-polar compounds:
 Insoluble/ Immiscible in water

 Polar compounds: haloalkane

 Intermolecular forces in polar compounds:
 Insoluble/ Immiscible in water

 Compounds that contains O atom:

 E.g.: Carbonyl compound (Functional group: C=O group, i.e: aldehyde and ketone),
ester (R–COO–R’) amide (R–COO–NH2), ether (R–O–R’)
 Total number of carbon atoms in the molecule ≤ 4 (n = 1, 2, 3 or 4):
 Total number of carbon atoms in the molecule > 4 (n = 4, 5, 6, ...):
TUTORIAL: Solubility
1. Which of the following compounds are soluble in water?
(a) CH3CH2CH2CH2CH3 (n) CH3CH2OCH2CH3
(b) CH3CHO (o) CH3CH2CH2NH2
(c) CH3COCH3 (p) CH3CH2CH2CH2OH

(d) OH (q) COCl

(e) CH3CH2OH (r) CH3CH2COOCH2CH3
(f) CH3COOCH3 (s) HCOOCH3
(g) CH3CH2CH2COOH (t) CH3CH2Cl

(h) Cl (u) CH3

(i) CH3CH2CH2CH2CONH2 (v) CH3CH2CH2COCH3
(j) CH3CH2CH2CH2CN (w) CH3CH2NH2
(k) CH3CH2COOCH2CH3 (x) C2H5OC2H5
(l) CH3CH2CH2CH2CHO (y) CH3CONH2

(m) COOH (z) CHO

2. Arrange the following compounds in increasing order of solubility in water.

OH CH3CH2CH2OH HOCH2CH2OH

3. Which of the following compounds is insoluble in benzene?

A CH3CH2NH 2 B NH2 C CH3CH2COOH
CH3CHCOOH
D CH3CONH2 E CH3CH2CH2CN F CH3CH2CH2Br

STRUCTURE AND ITS EFFECT ON ACIDITY & BASICITY

MESOMERIC EFFECT EFFECT OF STRUCTURE
INDUCTIVE EFFECT

 INDUCTIVE EFFECT:
 An electronic effect transmitted by successive polarisation of the  bonds within a
molecule.
 POSITIVE INDUCTION EFFECT/ ELECTRON DONATING EFFECT/
ELECTRON REPELLING EFFECT:
 Electro species  e.g.:
 NEGATIVE INDUCTION EFFECT/ ELECTRON WITHDRAWING EFFECT:
 Electro species  e.g.:
 RESONANCE EFFECT/ MESOMERIC EFFECT:
 Electron distribution/ delocalisation.
 Usually occurs in the following structures:

STRUCTURE AND ITS EFFECT ON ACIDITY

 The strength of an acid is measured by the extent it donates a proton to water.
 E.g.: IUPAC naming
 HCOOH + H2O (conjugate bases):

 CH3COOH + H2O Origin -suffix

(Acid)
 CH2ClCOOH + H2O
Carboxylic -oate
 CHCl2COOH + H2O acid
 CCl3COOH + H2O
Alcohol -oxide

 OH + H2O

 CH3OH + H2O
 CH3CH2OH + H2O

 By referring to the acid dissociation Recall concept of the stability of Nucleophile:

equations in the above, the more an acid
ionise in water (i.e. the further the
equilibrium position lies to the RHS),
 the the [H3O+]
 conjugate base is more
 the the acid.
1° > 2° > 3°
 An anion is stabilised by lowering its charge density.
 Positive inductive (electron donating) effect by alkyl
groups destabilises the anion  Because negative
charge density on anion
.  Negative inductive (electron withdrawing) effect by
electronegative species stabilises the anion Because
negative charge density on anion

 Example 1: Acidic strength: H2O > CH3OH

inductive effect of –CH3
 Electron density on oxygen atom in CH3OH:
 Stability of CH3O–
 Extent of dissociation in water:

 Example 2: Acidic strength: CH3OH > CH3CH2OH

inductive effect of –CH2CH3 is stronger
 Electron density on oxygen atom:
 Stability of conjugate base:
 Extent of dissociation in water:
 Example 3: Acidic strength: CH3CH2CH2OH > C(CH3)3OH
inductive effect of three –CH3 is stronger than one –CH2CH2CH2CH3
 Electron density on oxygen atom:
 Stability of conjugate base:

 Example 4: Acidic strength: OH > R–OH (aliphatic alcohol)

inductive effect of –R  Stability of RO–

 In O-, lone electron pair on oxygen atom is into

benzene ring 
stabilisation of O-
 Electron density on oxygen atom:

 Stability of conjugate base:

 Extent of dissociation in water:

 Example 5: Acidic strength: CH3COOH > CH3CH2OH
inductive effect of CH3CH2–  Stability of CH3CH2O–
effect of –C=O  Stability of CH3COO–
 Electron density on oxygen atom:
 Stability of conjugate base:
 Extent of dissociation in water:

 Example 6: Acidic strength: CH3COOH > OH

 The presence of benzene ring in OH and –C=O causes

stabilisation of O- and CH3COO–

 In both O- and CH3COO–, lone electron pair of oxygen atom is

 Diagram:

 But, oxygen atom is electronegative than carbon atom. Hence, resonance effect
(delocalisation of negative charge) of –C=O is than benzene ring.
 Electron density on oxygen atom:
 Stability of conjugate base:

 Extent of dissociation in water:

 Example 7: Acidic strength: Cl OH > OH

inductive effect of chlorine atom  Stability of Cl

O-
 Electron density on oxygen atom:

 Stability of conjugate base:

 Extent of dissociation in water:

Cl
 Example 8: Acidic strength:
OH > Cl OH

Cl
 Chlorine atom is nearer to –OH in
OH inductive effect of
chlorine atom is
 Electron density on oxygen atom:

 Stability of conjugate base:

 Extent of dissociation in water:

Cl
 Example 9: Acidic strength: > Cl OH
Cl OH
Cl
inductive effect of 2 chlorine atoms in
Cl is
OH

 Electron density on oxygen atom:

 Stability of conjugate base:

 Extent of dissociation in water:

 Example 10: Acidic strength: NO2 OH > Cl OH

 –NO2 is electronegative than chlorine atom

inductive effect of –NO2 is than chlorine atom

 Electron density on oxygen atom:

 Stability of conjugate base:

 Extent of dissociation in water:
 Example 11: Acidic strength: CH3CHClCOOH > CH3CH2COOH
inductive effect of chlorine atom  Stability of CH3CHClCOO–
 Stability of conjugate base:
 Extent of dissociation in water:

 Example 12: Acidic strength: CH3CHFCOOH > CH3CHClCOOH > CH3CHBrCOOH

 Electronegativity of substituents:
inductive effect of substituents:
 Stability of conjugate base:
 Extent of dissociation in water:

 Example 13: Acidic strength: CH3CCl2COOH > Important fact:

CH3CHClCOOH Acid 1 is stronger than Acid 2:
inductive effect of two chlorine atoms is  Ka1 Ka2
than one chlorine atom.  pKa1 pKa2
 Stability of conj. base:  [H3O+]:
 Extent of dissociation in water:  pH:

SUMMARY:

Acid strength: RCOOH > OH > H2O > ROH

EFFECT OF INDUCTIVE EFFECT AND MESOMERIC EFFECT ON ACID STRENGTH

ELECTRON ACCEPTORS ELECTRON DONORS MESOMERIC EFFECT

 e.g.: –X, –NO2, –C6H5  e.g.: –R Delocalisation of electrons in
 exerts negative inductive  exerts positive inductive  e.g.: ,
effect (–I effect) / electron effect (+I effect) / electron
withdrawing effect repelling effect (–C6H5)

Increases acid Decreases acid Increases acid

strength strength strength

 CH2ClCOOH is a stronger  CH3COOH is a  C6H5OH is a stronger

acid than CH3COOH weaker acid than acid than CH3OH
HCOOH  CH3COOH is a stronger
 CH3OH is a weaker acid than CH3OH
acid than H2O
STRUCTURE AND ITS EFFECT ON BASICITY (CONSIDERING LEWIS DEFINITION
OF BASES)
 The strength of a Lewis base is measured by the availability its lone pair of electrons on its
nitrogen atom to be donated to a proton.
 E.g.:
 NH3 + H2O
 CH3NH2 + H2O
 CH3CH2NH2 + H2O
 (CH3)2NH + H2O

 NH2 + H2O

 By referring to the equations in the Recall concept of the stability of Electrophile:

above, the more a base ionise in water 1° < 2° < 3°
(i.e. the further the equilibrium position  A cation is stabilised by lowering its charge density.
lies to the RHS),  Positive inductive (electron donating) effect by
alkyl groups stabilises the cation  Because its
 the the [OH–]
positive charge density
 conjugate acid is more .  Negative inductive (electron withdrawing) effect by
electronegative species destabilises the cation 
 the the base.
Because its positive charge density

Important fact:
 Example 1: Basic strength: CH3NH2 > NH3
Base 1 is stronger than Base 2:
inductive effect of –CH3
 Kb1 Kb2
 Electron density on nitrogen atom in CH3NH2 :
 pKb1 pKb2
 The ease in donating lone electron pair to a proton:  [OH–]:
 pOH:
 Stability of conjugate acid: .  pH:

 Example 2: Basic strength: CH3CH2NH2 > CH3NH2

inductive effect of –CH2CH3 is stronger than –CH3
 Electron density on nitrogen atom:
 The ease in donating lone electron pair to a proton:
 Stability of conjugate acid :
 Example 3: Basic strength: CH(CH3)2NH > CH3CH2CH2NH2
inductive effect of two –CH3 is stronger than one –CH2CH2CH3
 Electron density on nitrogen atom:
 The ease in donating lone electron pair to a proton:
 Stability of conjugate acid :
 Example 4: Basic strength: CH3CH2CH2NH2 > CH3CHClCH2NH2
inductive effect of chlorine atom  Stability of CH3CHClCH2NH3+
 Electron density on nitrogen atom:
 The ease in donating lone electron pair to a proton:
 Stability of conjugate acid :

 Example 5: Basic strength: R–NH2 (aliphatic amine) > NH2

inductive effect of –R  Stability of RNH3+

effect of benzene ring  lone electron pair on nitrogen atom is delocalised into benzene
+
ring  stability of NH 3

 Electron density on nitrogen atom:

 The ease in donating lone electron pair to a proton:

 Stability of conjugate acid :

 Example 6: Basic strength: NH2 > Cl NH2

inductive effect of chlorine atom  Stability of Cl

NH3+
 Electron density on nitrogen atom:

 The ease in donating lone electron pair to a proton:

 Stability of conjugate acid :

 Example 7: Basic strength: CH3 NH2 > NH2

inductive effect of –CH3  Stability of CH3 NH3+

 Electron density on nitrogen atom:

 The ease in donating lone electron pair to a proton:

 Stability of conjugate acid :

 TUTORIAL:
21: 3. Acidity of carboxylic acids

3.1 a. Arrange the following compounds in increasing of pKa values:

b. Match the acids in each set with the pKa values given within brackets.

SUMMARY:

RNH2 > NH3 > NH2

EFFECT OF INDUCTIVE EFFECT & MESOMERIC EFFECT ON BASIC STRENGTH

ELECTRON ACCEPTORS ELECTRON DONORS MESOMERIC EFFECT

 e.g.: –X, –NO2, –C6H5  e.g.: –R Delocalisation of electrons in
 exerts negative inductive  exerts positive inductive  e.g.: (–C6H5)
effect (–I effect) / electron effect (+I effect) / electron
withdrawing effect repelling effect
 Decreases basic Increases basic Decreases basic
strength strength strength

 CH2ClNH2 is a weaker  CH3NH2 is a stronger  C6H5NH2 is a weaker

base than CH3NH2 base than NH3 base than CH3NH2
 Must know for the MCAT

Stereochemistry Stereochemistry involves the study of the relative spatial arrangement of atoms within molecules.

Chiral The term chiral is used to describe an object that is non-superimposable on its mirror image.

Cis-trans Cis-trans isomerism is a form of stereoisomerism describing the orientation of functional groups typically
isomerism around double bonds which cannot rotate.

Steric effects Steric effects arise from the fact that if atoms are brought too close together, there is an associated cost in
energy due to overlapping electron clouds.

Enantiomer Enantiomers are stereoisomers that are nonsuperimposable complete mirror images of each other.

Racemic A racemic mixture is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule.

Diastereomer Diastereomers are stereoisomers that are not enantiomers.

Optical activity Optical rotation or optical activity is the rotation of linearly polarized light as it travels through certain
materials.

Meso compound A meso compound is a chemical compound with molecules that contain 2 or more stereocenters but which is
optically achiral because it contains an internal plane of symmetry.

Newman A Newman projection visualizes chemical conformations of a carbon-carbon chemical bond from front to
projection back, with the front carbon represented by a dot and the back carbon as a circle.

Staggered A staggered conformation is a chemical conformation that exists in any open chain single chemical bond
conformation connecting two sp3 hybridised atoms as a conformational energy minimum.

Eclipsed An eclipsed conformation is a chemical conformation that exists in any open chain single chemical bond
conformation connecting two sp3 hybridised atoms as a conformational energy maximum.

Stereocenter A stereocenter is any atom in a molecule bearing groups such that an interchanging of any two groups leads
to a stereoisomer.

Conformational Conformational isomerism is a form of stereoisomerism involving molecules with the same structural
isomerism formula existing as different conformers due to atoms rotating about a bond.

Van der Waals Van der Waals strain results from van der Waals repulsion when two substituents in a molecule approach
strain each other with a distance less than the sum of their van der Waals radii.
 Cyclohexane Cyclohexane is a cycloalkane containing 6 carbons and 12 hydrogens, which has the lowest angle and
torsional strain of all the cycloalkanes.

Angle strain The presence of angle strain in a molecule indicates that in a specific chemical conformation bond angles are
deviating from the ideal bond angles required to achieve maximum bond strength.

Should know for the MCAT

Ring strain Ring strain is an organic chemistry term that describes the destabilization of a cyclic molecule-such as a
cycloalkane-due to the non-favorable high energy spatial orientations of its atoms.

Chiral resolution Chiral resolution in stereochemistry is a process for the separation of racemic compounds into their
enantiomers.

Prochiral Prochiral molecules can be converted from achiral to chiral in a single step.

Hyperconjugation Hyperconjugation is the stabilizing interaction that results from the interaction of the electrons in a sigma
bond with an adjacent empty or partially filled non-bonding p-orbital or antibonding pi orbital leading to an
extended molecular orbital that increases the stability of the system.

Anomeric effect The anomeric effect or Edward-Lemieux effect describes the tendency of heteroatomic substituents adjacent
to a heteroatom within a cyclohexane ring to prefer the axial orientation instead of the expected, less-
hindered equatorial orientation.

Enantiomeric Enantiomeric excess exists where one enantiomer is present more than the other in a chemical substance.
excess

May appear in context in MCAT passages - advanced terminology

Baeyer strain Baeyer strain theory explains specific behaviour of chemical compounds in terms of bond angle strain.
theory

Enantiomer self- Enantiomer self-disproportionation is a process describing the separation of a non-racemic mixture of
disproportionation enantiomers in an enantioenriched fraction and a more racemic fraction.

Homochirality Homochirality is a term used to refer to a group of molecules that possess the same sense of chirality with
similar groups are arranged in the same way around a central atom.

Chiral pool Chiral pool synthesis is a strategy that aims to improve the efficiency of chiral synthesis by beginning from a
synthesis stock of readily available enantiopure substances.

Asymmetric Asymmetric induction describes the preferential formation in a chemical reaction of one enantiomer or
 induction diastereoisomer over the other as a result of the influence of a chiral feature present in the substrate, reagent,
catalyst or environment.

Chiral auxiliary A chiral auxiliary is a chemical compound or unit that is temporarily incorporated into an organic synthesis
so that it can be carried out asymmetrically with the selective formation of one of two enantiomers.

Circular Circular dichroism is a form of spectroscopy based on the differential absorption of left- and right-handed
dichroism circularly polarized light.