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CHEMISTRY FORM 6

ORGANIC CHEMISTRY
CHAPTER 1 :
CARBON COMPOUND

1.1
The Chemistry of Carbon
 Organic Chemistry ~ branch of chemistry concerning
compound of carbon (except CO, CO2, CO32-)
Aliphatic
compounds
Open chain
organic
compounds.
Do not have
special stability
like benzene.
Compound may
be unbranched
or branched
 Alkane, alkene,
alkyne,
haloalkane

Alicyclic
compounds
Closed ring of
organic
compounds.
Rings may
contain single or
double bonds
Compound may
be branched or
unbranched
 Cyclohexane,
cyclobutene

Aromatic
compounds
Contain at least
one benzene
ring (those with
in it)

Heterocyclic
compounds
Closed ring
contain element
other than
carbon in it (like
N, S, O)

 Phenol,
naphthalene,
toluene

 Pyridine

1.
Hybridisation of alkane, alkene and alkyne
14element. It has the electronic
 Carbon is a Group ___
configuration of ______________
1s2 2s2 2p2
The orbital diagram
 Ground state of C : _____
_____ _____ _____
2s
2p
Methane, CH4

Type of hybridisation :

Excited state of C : _____


2s

Hybridised state :

sp3

_____ _____ _____


2p

_____ _____ _____ _____


sp3

Ethene, C2H4

Type of hybridisation :

Excited state of C : _____


2s

Hybridised state :

_____ _____ _____


2p

_____ _____ _____

sp2
Molecular shape
Trigonal planar

Angle between bond


pair bond pair
120o

sp2

_____

pz

Ethyne, C2H2

Type of hybridisation :

Excited state of C : _____


2s

Hybridised state :

_____ _____ _____


2p

_____ _____

sp
Molecular shape
Linear

Angle between bond


pair bond pair
180o

sp

_____ _____

py

pz

As a conclusion, the formation of double bond


one bond () and
(C=C) is due to ______sigma
one ()
_____pi bond
 While the formation of triple bond (CC) is
one
due to ______sigma
bond () and _____pi
two ()
bond


Hybridisation in benzene
 Benzene (C6H6) is a flat and symmetrical molecule. All the
atom (6 C atom and 6 H atom) in a benzene molecule lie in the
same plane. The Carbon atoms are arranged in the form of
hexagon as shown in diagram at the left.
 The formation of benzene can be deduced using hybridisation
theory

Excited state of C : _____


2s

_____ _____ _____


2p

Hybridised state: _____ _____ _____


sp2

_____
pz

Since each carbon contribute an unhybridised electron, so the


side touch between CC atom will form a double bond. Hence
3 bond build between CC in benzene ring.
there are _____ double
In another words, there are free delocalise electrons move about
in benzene ring.
The following notes are taken into consideration when drawing
structure of benzene The unhybridised p orbitals do not overlap
in pairs to form double bonds alternating with 3 single bonds as
shown in Kekule structure.

hybrid
The structure of benzene is a .....
of 2 forms
The resonance hybrid of benzene can be expressed as
Unlike ethene, the double bond in benzene has a larger volume
(space) to delocalise electron. Hence the more space provided,
the lower the energy in benzene. This makes benzene posses
an extra stability.

1.2
 The
the
(a)
(b)
(c)
(d)

Chemical formulae of Organic Compound


formula of an organic compound can be represented by
empirical formula
molecular formula
structural formula
skeletal formula

Empirical formula of a compound shows the simplest ratio


of the atoms of each element in the compound.
 Molecular formula of a compound shows the actual number
of atoms of each element in the compound


1. Derive the empirical formula of a


hydrocarbon that on analysis gave the
following percentage composition: C =
85.63%, H = 14.37%. given the relative
molecular mass of the hydrocarbon is 84,
determine the molecular formula
Element

Mass

85.63

14.37

Mol

85.63
12
= 7.14 mol

14.37
1
=14.37 mol

Ratio

7.14/7.14
=1

14.37/7.14
=2

Empirical formula = CH2


(CH2)n = 84
(12 + 2(1))n = 84
n=6
Molecular formula = (CH2)6
= C6H12

2. A 1.367 g sample of an organic compound


was combusted in a stream of dry oxygen to
yield 3.002 g CO2 and 1.640 g H2O. If the
original compound contained only C , H, and
O, what is its empirical formula?
CxHyOz + mO2  x CO2 + y/2 H2O
Since 1 C = 1 CO2
x / 12 = 3.002 / 44 ; x = 0.8187 g
Since 2 H = 1 H2O
y / 2= 1.640 / 18 ; y = 0.1822 g
Mass of O, z
= 1.367 (0.8187 + 0.1822)
= 0.3661 g
Elemen

Mass

0.8187

0.1822

0.3661

Mol

0.8187
12
=0.0682

0.1822
1
=0.1822

0.3661
16
=0.0229

Ratio

0.0682/0
.0229
=3

0.1822/0
.0229
=8

0.0229/
0.0229
=1

Empirical formula = C3H8O

A 1.500 g sample of a compound containing


only C, H, and O was burned completely. The
only combustion products were 1.738 g CO2
and 0.711 g H2O. What is the empirical
formula of the compound?
CxHyOz + mO2  x CO2 + y/2 H2O
Since 1 C = 1 CO2
x / 12 = 1.738 / 44 ; x = 0.474 g
Since 2 H = 1 H2O
y / 2(1) = 0.711 / 18 ; y = 0.079 g
Mass of O, z
= 1.367 (0.474 + 0.079)
= 0.947 g
Elemen

Mass

0.474

0.079

0.947

Mol

0.474
12
=0.0395

0.079
1
=0.079

0.947
16
=0.0592

Ratio

0.0395/0
.0395
=1

0.079/
0.0395
=2

0.0592/
0.0395
= 1.5

Empirical formula = C2H4O3

Elementary analysis showed that an organic


compound contained C, H, N, and O as its
elementary constituents. A 1.279-g sample was
burned completely, as a result of which 1.60 g
of CO2 and 0.77 g of H2O were obtained. A
separately weighed 1.625 g sample contained
0.216 g nitrogen. What is the empirical
formula of the compound?
Since 1 C = 1 CO2
x / 12 = 1.60 / 44 ; x = 0.4364g
Since 2 H = 1 H2O
y / 2(1) = 0.77 / 18 ; y = 0.08556 g
Since 1.625 g of same sample produce
0.216 g of nitrogen
Mass of N in sample, n
n / 1.279 = 0.216 / 1.625
n = 0.17 g
Mass of O, z
= 1.279 (0.4364 + 0.08556 + 0.17)
= 0.587 g
Empirical : C3H7NO3

Structural formula of an organic compound is the formula which


shows how the atoms are bonded together as well as the
numbers of each atom present. Structural formula can be
expressed in a few ways.
 Example : butane, C4H10


b) Displayed formula

a) Shorthand
CH3CH2CH2CH3

c) 3-D @
stereochemical

d) Skeletal formula

c) 3-D @
stereochemical

d) Skeletal formula

e) Simplified notation
CH3(CH2)2CH3


Example

: 2-methylhexane

a) Shorthand
CH(CH3)2CH2CH2CH2CH3
b) Displayed formula

Example :

4,4-dimethylpent-2-ene

a) Shorthand

C(CH3)3CH=CHCH3
b) Displayed formula

c) 3-D @
stereochemical

d) Skeletal formula

Example :

3-ethyl-2,4-dimethylhexane

a) Shorthand

CH(CH3)2CH(CH2CH3)CH(CH3)CH2CH3

c) 3-D @
stereochemical

d) Skeletal formula

b) Displayed formula

Example :

2,2,5-trimethylhex-3-yne

a) Shorthand

C(CH3)3CCCH(CH3)2
b) Displayed formula

c) 3-D @
stereochemical

d) Skeletal formula

1.3









Classification of Organic Compounds based on the


Functioning Group and its General Formulae
Homologous series ~ compounds with similar chemical
properties in which each member differs from the previous
one by addition of CH2. The characteristic of a homologous
series are as follow.
All compounds in homologous series has the same functioning
group and chemical properties
Each member differ from the next series by a CH2 group, in
another words, molecular mass of each compound in series
14
differ from next by
All the compounds in the series may be prepared by using the
similar methods.
Physical properties show a progressive change with increase
of molecular mass.
All the compounds in the series contain same elements and
functioning group, thus it can be represented by same general
formula.

Homologous
series
Alkanes

RH

Examples +
Structural formula

General
formula
pentane
CnH2n+2

Cycloalkane

CH3CH2CH2CH2CH3

heptane
CH3CH2CH2CH2CH2CH2CH3

cyclobutane

Cyclohexane

hex-1-ene

but-2-ene

CnH2n

Alkenes

RCH=CHR

CnH2n

CH2=CHCH2CH2CH2CH3

cyclohexene

Cycloalkene
CnH2n2

CH3CH=CHCH3

cyclobutene

Alkynes

RCCH

propan-1-ol

pentan-3-ol

Butanal

hexanal

Propanone

heptan-3-one

CnH2nO

Ketone

RCOR

2-bromopentane

CnH2n+1OH /
CnH2n+2O

Aldehyde

RCOH

1-chlorobutane
CnH2n+1X
(X = Cl, Br, I)

Alcohol

ROH

pent-1-yne

CnH2n2

Haloalkane

RX

Propyne

CnH2nO

Carboxylic
acid

RCOOH

propyl butanoate

ethylamine

butylamine

propylamide ;

pentylamide

CnH2n+1NH2

Amide

RCONH2

ethyl ethanoate ;
CnH2n+1COO
CmH2m+1 /
CnH2nO2

Primary
amine

RNH2

pentanoic acid

CnH2n+1COOH
CnH2nO2

Ester

RCOOR

butanoic acid ;

CnH2n+1CONH2

1.4
Alkyl and Type of Alkyl groups
 Alkyl group ~ obtained by removing a hydrogen atom from an
alkane.
 Symbol of alkyl is R, where R has the general formula of
CnH2n+1.

Alkane

Alkyl

Alkane

Alkyl

Methane

Methyl

CH3

Ethane

Ethyl

C2H5

Propane

Propyl

C3H7

Butane

Butyl

C4H9

C5H11

Hexane

Hexyl

C6H13

Pentane

Pentyl

Alkyl can be categorise into 3 groups


Type of alkyl
group

Example

Comment

Primary

Only one alkyl group attached to carbon


atom

Secondary

Two alkyl group attached to carbon atom

Tertiary

Three alkyl group attached to carbon


atom

1.5
Isomerism in Organic Compound
 Isomers ~ substances which have the same molecular formula
but different molecular structure
Isomerism

Structural
isomerism

Chain
isomerism

Position
isomerism

Stereoisomerism

Functional
isomerism

Geometrical
isomerism

Optical
isomerism

1.5.1 Structural Isomerism


 ~ are isomers with same molecular formula but different
structural formula (link differently)
 As mentioned above, structural formula can be separate into 3
different categories
Chain isomerism
Positional isomerism
Functional group isomerism

1. Chain isomerism ~ isomers which have different carbon chain


(straight or branched chain)
Pentane (C5H12)

Butan-1-ol (C4H9OH)

CH3CH2CH2CH2CH3

CH3CH2CH2CH2OH
C(CH3)4
CH(CH3)2CH2OH

CH3CH2CH(CH3)2

1-chloropentane (C5H11Cl)

Hexanal (C6H12O)

CH(CH3)2CH2CH2CHO

CH3CH2CH2CH2CH2CHO

CH3CH2CH2CH2Cl
CH3CH2CH(CH3)CH2Cl

C(CH3)3OH

C(CH3)3CH2CHO
C(CH3)3CH2Cl
CH(CH2CH3)2CHO

2. Position isomerism ~ isomers which the position of


functioning group is different
Hexene (C6H12)

Bromohexane (C6H13Br)
CH3CHBrCH2CH2CH2CH3

CH2=CHCH2CH2CH2CH3 CH3CH=CHCH2CH2CH3

CH3CH2CH=CHCH2CH3
Pentanol (C5H11OH)

CH3CH2CH2CH2CH2OH

CH3CH2CH2CH(OH)CH3

CH3CH2CH(OH)CH2CH3

CH2BrCH2CH2CH2CH2CH3

CH3CH2CHBrCH2CH2CH3
Dichlorobenzene (C6H4Cl2)

3.
Functional isomerism ~ isomers which has the same
molecular formula but different molecule with different
functioning group.
Alkene and cycloalkane C5H10

Alcohol and ether C4H10O

Aldehyde and ketone C6H12O

Carboxylic and ester C7H14O2

1.5.2 Stereoisomerism
 Geometrical Isomerism ~ same structural formula but different
spatial arrangement.
~ also known as cis-trans isomer
~The essential requirement for the existence of geometrical
isomerism in organic compound must contains a carbon carbon
double bond (C=C)
~ A ring structure which hinders the rotation of a CC single
bond in a ring.
 However, cis-trans isomers cannot occur if one of the carbon
atoms in the double bond has 2 identical atoms / groups.
1,2-dichloroethene

1,1-dichloroethene

pent-2-ene

1,2-dimethylcyclobutene

But-2-ene-1,4-dioic acid

1,4-dichlorocyclohexane

Physical Properties of Geometric Isomers


 Cis-isomer usually has a lower melting point as the
structure of cis-isomer is less symmetrical. Therefore, cisisomer cannot be closely packed in the crystal lattice
resulting the intermolecular forces to become weaker than
in trans-isomer.
 On the other hand, cis-isomer has a higher boiling point
because the space arrangement in cis isomer caused the
compound to become a polar molecule. As a result, the
intermolecular forces fo cis-isomer in liquid is stronger,
causing the temperature required to boil the substance
become higher. Trans-isomer on the other hand, has 0
dipole moment.

(2)
Optical isomerism
 Optical activity is the ability of certain crystal or solution of
certain substances to rotate the plane of plane-polarised light.
Such substances are said to be optically active (sometimes
are known as chiral molecule)
 Optical isomers are optically active substances which possess
the same molecular structure but different in their effect
on plane polarised light.
 For an optically active isomer, the object and mirrored image
cannot be superimposable to one and another. Example, in 1bromo-1-chloro-1fluoromethane (CHClBrF), it shows optical
active when brought to plane-polarised light.

An organic molecule will exhibit optical isomerism if it contains


one chiral carbon atom.
 Chiral carbon atom is a carbon atom which is attached by 4
different atoms / groups.
 Also known as asymmetrical carbon often shown as C*
 Example : State whether the organic compound below exhibit
optical isomerism. If yes, mark * at chiral carbon atom.


CH3CH2CH(Cl)CH3

C(CH3)2(Br)(OH)

CH3CBr=CH2

HOCH2CH(NH2)COOH

CH3CH2CH(OH)CH3

1.6 Lewis Acid & Lewis Base : Nucleophiles and Electrophiles


Substance which receive lone pair electron
 Lewis Acid :
Substance which donate lone pair electron
 Lewis Base :

Ammonia react with


hydrogen ion to form
ammonium ion

Boron trifluoride react


with ammonia to form
a complex

Aluminium trichloride
react with chloride ion
to form
tetrachloroaluminate
ion

Water molecule
attached to cobalt ion
to form
hexaaquacobalt (III)
ion.

Methylamine react with


water to form a basic
solution

Ethanoic acid react


with water to form
ethanoate ion and
hydroxonium ion

In organic reaction, such reaction can be classified as either


nucleophile or electrophile, depending on whether they
attack regions of high electron density ( ) or region with low
electron density ( +)
Nucleophile

Definition

Examples

Electrophile

Nucleo = nucleus ; phile = love


Nucleophile mean love nucleus. In
terms of Lewis acid-base theory,
nucleophiles are often Lewis base,
which donate lone pair electron.

Electro = electron ; phile = love


Electrophile mean love electron. In
terms of lewis acid-base theory,
electrophiles are often Lewis acid,
which accept lone pair electron.

:OH

RO:

:Cl

H+ (H3O+)

NO2+

Cl2 ; Cl+

:Br

:I

CN:

Br2 ; Br+

I2 ; I+

carbonium

:C
carbanion

ROH

C=C

RN2+

R3C+

BF3

:NH2

RNH2

H2O

AlCl3

FeBr3

ZnCl2

1.7
Inductive Effect and Mesomeric Effect
 Inductive effect is defines as the shift in electron density from one
atom to another to form a polar bond.
 For example, in the bonding of CCl. In the presentation of inductive
effect, the arrow shows that carbon atom repel electrons
+

Chlorine atom attract the electrons as it has a higher elctronegativity


1.7.1 Electronwithdrawing group
 Most atoms and groups of atoms are more electronegative than carbon
atom, thus withdraw electron from carbon. When this occurs,
atoms/molecules are said to exert a negative inductive effect (I
effect).
 Example of electron withdrawing group


Cl ; Br
;I

NO2

CN

COOH

COOR

C=O

SO3H

C6H5

1.7.2 Electron donating group


 Some atoms/groups are less electronegative than carbon thus
donate electrons to carbon atom. These atoms/groups are also
known as electron donating group and they exert a positive
inductive effect (+I effect). Alkyl group are known to have a +I
effect. The effect increase with the increase of alkyl group
attached to the C atom.
 The inductive effect produces a permanent dipole and this will
influence its physical properties such as boiling / melting point,
acid and basic strength, reaction of functional group and rate of
reaction.
 Inductive effect may also occur when there is a permanent shift
of electron due to the polarisation of sigma bond (-bond). The
shift of electron can also occur in a pi () bond. The shift of
electron in multiple bonds toward a more electronegative atom is
known as resonance effect (mesomeric [M] effect)

Example in methanal, oxygen atom is more electronegative


than carbon atom. Consequently, the electron shifted to
oxygen atom. The structure can be represented as a resonance
hybrid between structure I and II.

Same phenomenon can occur in carboxylate anion. M-effect


play an important role in the structure and stability of many
compounds. The electrons are spread and delocalised over
the carbon and oxygen atoms. We can represent the
delocalisation of electrons in carboxylate ion as follow

1.8

Type of chemical reaction in Organic Chemistry

Type of Organic
Reaction
Substitution

Addition

Elimination

Definition : one or
more atom / group is
substitute by another
atom / group of atoms

Definition : a small
Definition : 2 reactants atom / group is
react together and
removed (eliminated)
form 1 product
from the molecule
involve

Example :
CH3CH2Cl + OH 
CH3CH2OH + Cl

Example :
CH2=CH2 + Br2 
CH2(Br) CH2(Br)

Example
CH3CH2OH 
CH2=CH2 + H2O

1.9 Bond Fission ~ Ways of Breaking Chemical Bond


 In a covalent bond, a pair electron is shared between 2 atoms.
When the covalent breaks, these 2 electrons are redistribute
between 2 atoms. There are 2 ways how these electrons are
redistribute.
Bond fission
Homolytic fission
The 2 shared electrons distribute
evenly between the 2 atoms
Free radicals are formed after
homolytic fission and it is usually
represented by X
Since it is a single electron, free
radicals tend to become unstable,
thus are reactive.
Example :
Cl Cl  2 Cl (chlorine radical)
H3CH 
CH3
+
H
methyl radical hydrogen radical

Heterolytic fission
o Shared electron in the covalent bond
only goes to one of the atom. The pair
of electron usually goes to the atom
with higher electronegative
o Eventually, one will become negatively
charged (as a result of receiving extra
electron) while the other become
positively charged (lose electron to the
other party)
o Example :
Cl Cl  :Cl + Cl
(CH3)3CBr  :Br + (CH3)3C

Practice
1.Base on the molecular structure, draw the hybridisation diagram
of the following molecules, state the type of hybridisation and its
shape, and state the angle of each hybridised structure
a) CH3CH=CHOH

b) CHCCH2NH2
H

Displayed formula

Short hand / notation

CH(CH3)2C(CH3)2CH2CH2CH3

C(CH3)3CH(CH2CH3)2

CH(CH3)2CH(CH3)CH=C(CH3)2

CH(CH3)2CH(OH)CH(CH2CH3)2

Skeletal formula

CH2(NH2)CH(C6H5)CONH2

COHCH(Br)C(CH3)2CH2COOH

COHC(CH3)2CH(OH)CCCH3
COOHCH(CH3)CH2C(CH3)(CH2CH3)CH2CH(OH)(CH3)

Name the functioning group presence


Alkene,
alcohol,
aldehyde

CH2ClCOCH2CHNH2CH2CH2CONH2

Haloalkane,
Ketone ;
Amine ,
Amide
Aldehyde ;
Alcohol ;
Alkyne
Carboxylic acid

Molecules

Type of
isomerism

geometrical

geometrical

Optical

Diagram of isomers

CH2ClCH=C(CH3)CH2COOH

geometrical
geometrical

optical

optical

Particles

Particles

Particles

Br2

electrophile

Br+

electrophile

Br-

nucleophile

NH3

nucleophile

CH3NH2

nucleophile

NH2+

electrophile

CH3-

nucleophile

CH3COH

electrophile

CH3+

electrophile

nucleophile

nucleophile

electrophile

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