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COURSE CODE:
CHM 121
LECTURER:
AJANI O.O.
What is hybridization?
Hybridization in carbon atom systems
Homologous series: introduction and characteristics.
Various classes of functional groups.
General and selective tests for some functional groups.
Some carboxylic acid derivatives.
Isomerism - both structural and stereoisomerism.
Ordinary and plane polarized light.
bond pair (BP), the compound shows the normal shape peculiar to its
hybridization pattern. However, when there is lone pair (LP), there will be
slight distortion to give it another shape because the lone pair (LP) tends to
re-orientate itself in order to minimize repulsion. The order of the repulsive
power is: LP-LP > LP-BP > BP-BP. This is established by Valence Shell Electron
Pair Repulsion Theory (VSEPAR).
Determination of Hybridization Pattern
Write out the ground state (GS) valence electronic configuration of
central atom.
Promote the excited state (ES) in such a way to accommodate
electrons from surrounding groups or atoms.
Pair each electron from the surrounding atoms with each half-filled
suborbital level of the central atom to have fully filled configuration at
each suborbital level.
Write out the valence suborbital level at this stage as the hybrid
orbital.
You can then predict the shape, bond angle and some other factors as
shown in the table below:
Total
Electron
Pair
No of
No of
Bond Pair Lone Pair
(BP)
(LP)
Geometrical
Distribution
or Shape
Ideal
Bond
Angle
Typical
Example
Hybri
d
orbita
l
sp
Linear
180O
BeCl2
3
3
3
2
0
1
sp2
sp2
Trig. Planar
Trig. Planar
120O
120O
BF3
SiO2
4
4
4
4
3
2
0
1
2
sp3
sp3
sp3
Tetrahedral
Trig.
Pyramid
Angular/Ben
t
109.5o
107 o
104.5 o
CH4
NH3
H2O
5
5
5
5
5
4
3
2
0
1
2
3
sp3d
sp3d
sp3d
sp3d
90o, 120o
90o, 120o
120o
180o
PCl5
SF4
ClF3
XeF2
6
6
6
5
0
1
sp3d2
sp3d2
Trig.
Bipyramid
Trig.
Pyramid
Trig. Planar
Linear
Octahedral
Sq. pyramid
90o
90o
SF6
BrF5
sp3d2
90o
Sq. planar
XeF4
Solution:
(i)
3S2
3d1
3P4
3S2
(iii)
Each of the up spin half filled sub-orbital accepts each of the 4down
3S2
3P4
3d1
(iv)
(v)
Hybridization in Carbon
2s + 2p2
2s + 2p
C
X
PX
PY
Energy
PZ
after blending
SP3
SP3
SP3
SP3
3-D Structure
Orbital picture
unhybridize
PY
PZ
after blending
SP2
SP2
SP2
Sp Hybridization in Carbon
5
The carbon 2s orbital combines with one of its 2p orbital (i.e. 2px) to
generate two sp hybrid orbitals of equivalent energy which are linear in
shape with bond angle of 180o. The remaining two 2p (i.e. 2py, 2pz) are
unhybridized. This sp hybrid orbital has 50% s and 50%p character. Carbon
will be sp-hybridized when it is directly linked to two atoms in a neutral
molecule e.g.
Energy Level Diagram
PX
PZ
PY
Unhybridized
PY
PZ
after blending
SP
SP
Orbital Picture
3D-Structure
(ii) Overlap of a hybrid orbital and s orbital e.g. sp3-s, sp2-s, sp-s. This is
seen in carbon-hydrogen bone of methane and other alkanes.
C
H
1s
(iii)
Orbital Picture
3D-Structure
Cl
Orbital Picture
Cl
3D-Structure
Pi bond: can only be formed when two adjacent carbons are unhybridized.
It is a covalent bond formed as a result of lateral overlap of two unhybridized
p-orbitals on adjacent carbon atoms.
Pi-bond
Sp3-sp3 Overlap in Ethane (C2H6)
H
H
3D-Structure
Orbital Picture
Pi bond
120o
C
The electrons in the -bond are called electrons while those in the -bond
are called electrons. Since -bond is weaker than -bond, the bond energy
of C=C is less than twice the bond energy of C-C.
Rotation about C=C is restricted unlike that involve in C-C which is free. The
bond length is 1.34 (shorter because of higher electron density).
Sp-sp Overlap in Ethyne (C2H2)
Overlap of sp-sp hybrid orbital of two carbon atoms gives rise to a triple bond
(C C), which has 1 +2-bonds. The 2-bonds are product of lateral overlap
of two unhybridized p orbitals (i.e. 2py, 2pz) of one sp carbon with that of
other as seen in ethyne (C2H2). The whole of ethyne in summary, has 3 + 2
bonds.
Pi-bond
H
sigma
C
sigma
180o
H
sigma
3D-Structure
Orbital Picture
Pi-bond
Example 2: Assuming the normal bond angle at sp3, sp2 and sp hybridized
carbon atom, draw the graphical formula of each of the following compounds
in 3-Dimensional representation.
(i) CH3CH2 C CCH=CH2 (Hex-1-en-3-yne)
(ii) H2C=C(CH3)CH=CH2 (2-Methylbuta-1,3-diene or isoprene)
(iii)
CH3CH=CHCH2 C CH (Hex-4-en-1-yne)
(iv)
H3C
sp3
H
CH
CH2
sp3
sp
sp
sp2
sp2
H
a
a
H
CH2
C
a
H
C
e
a = b = 109.5o
c = d = 180o
e = f = 120o
C
f
H
Sp3-sp3 overlap
(ii)
Sp3-sp2
(iii)
Sp-p overlap
For example, alkane is a family of saturated hydrocarbon with its first four
members being methane (CH4), ethane (C2H6), propane (C3H8) and butane
(C4H10). Each of these hydrocarbons differs from its neighbor by a constant of
CH2- despite the fact that they are all alkanes; so, they are members of the
same homologous series.
CH4 + Na2CO3
C2H6 + Na2CO3
11
CO2 + 2H2O
7CO2 + 8H2O
17CO2 + 18H2O
(5). Physical properties of the members vary with change in the molecular
weight.
C1 C4 are gases at room temperature.
C5 C14 are liquid at room temperature.
C15 are above are solid at room temperature.
(ii)
3x + 3y 3z + xyz
(iv) x + y - 21zo
12
Suffix
General
Form.
Functional
Group
Typical
Example
Alkane
-ane
CnH2n+2
-C- paraffin
Methane
Alkene
-ene
CnH2n
C=C
Ethene
Alkyne
-yne
CnH2n-2
CC
Propyne
Alkoxy alkane
-ether R-O-R
-O- (ether)
Diethylether
Alkanol (Alcohol)
-ol
R-OH
-OH
(hydroxyl)
Ethanol (1o)
Alkanal (aldehyde)
-al
R-CHO
C=O
(carbony of
aldehyde)
ethanal
Alkanone (ketone)
-one
R-CO-R
C=O
(carbonyl of
ketone)
Propanone
(acetone)
Akanoic acid
(carboxylic acid)
-oic
acid
R-COOH
-COOH
(carboxylic)
Ethanoic acid
CH3COOH
Amine
amin
e
R-NH2
-NH2 (amino)
1o, 2o or 3o
Ethanamine
CH3CH2NH2
Alkene and alkyne will undergo a positive reaction and decolourize the
following reagents because of the presence of unsaturation whereas alkane
will not react with them.
Acidified potassium permanganate ( KMnO4/ H+).
Alkaline potassium permanganate ( KMnO4/ HO-).
Acidified potassium heptaoxochromate vi (K2Cr2O7/ H+).
Bromine water in carbon tetrachloride (Br2/H2O IN CCl4).
Hydrogen gas in finely divided Nickel catalyst (H2/Ni at 200oC).
However, to distinguish between alkene and alkyne, ammoniacal silver
nitrate or ammoniacal cupper oxide is employed. While alkene remains
unreactive in ammoniacal solution, terminal alkyne will react positively with
such solution.
CH2=CH2 + Br2/H2O
HO-CH2-CH2-Br
HO-CH2-CH2-OH
(ii)
R
O
C
H
Aldehyde
ketone
R'
14
R
R'
C O+
H
NH2 N
NO2
R'
O2 N
2,4-dinitrophenylhydrazine
H
N
NO2
+ H2O
O2N
corresponding hydrazone
Since, both aldehye and ketone have the same reaction with 2,4-DNP how
then can we distinguish between the two? This can be achieved by using
either Fehling or Tollens test; since aldehyde react positively with the two
reagents (Fehling and Tollens reagents) while ketone will not. Otherwise, you
can react ketone with semicarbazide (NH2NHCONH2) to obtain a coloured
precipitate of semicarbazone while aldehyde will not react with
semicarbazide.
(b).Fehling Solution Test
Add few drops of alkanal (aldehyde) to the blue coloured fehling solution and
warm; the mixture will turn to brick red precipitate whereas with alkanone
(ketone) the blue colour remains (i.e. no reaction).
This change is as a result of reduction of Cu+2 to Cu+1
RCHO + Cu+2
RCOONa + Cu+1
NaOH/H2O/warm
Blue
brick red
This is also what happens in test for glucose because it is a reducing sugar.
Glucose will give a positive reaction with fehling solution while fructose will
not. Fehling solution is a mixture of fehling A (CuSO4) and Fehling B (NaOH
and Rochelle salt).
(c).Tollens Test
This is otherwise called silver mirror test. Warming a mixture of aldehyde and
ammoniacal silver nitrate (Tollens reagent) gives a deposit of shining silver
metal on the wall of the test-tube whereas with carbonyl of ketone, there is
no reaction.
RCHO + Ag(NH3)2+
RCOO- + Ag
15
R-CH=CH-CHO
,-unsaturated aldehyde
R-CH=CH-COOH
,-unsaturated acid
16
OH
COCl
COOH
+
PCl5
benzoic
acid
POCl3
HCl
benzoyl
chloride
CH3COCl + POCl3(l) +
CH3COCl + SO2(g)
+ HCl(g)
CH3CONH2 + H2O
CH3CONH2 + NaCl
17
Ethanoyl chloride
ethanamide
2CH3COOH
(CH3CO)2O
O
CH3
CH3
P4O10
-H2O
CH3
C
O
CH3
C
O
H+
CH3COOCH2CH3 + H2O
Ethyl ethanoate
CH3COCl + CH3CH2OH
0-5oC
CH3COOCH2CH3 + HCl
18
NH
N
NH2
CH3
CH3
CO2H
4. With the aid of equation only, how can you synthesize 3-methyl-2pentenoic acid from 3-methyl-2-pentenal .
Isomerism
In 1823, transformation of ammonium cyanate (inorganic compound) to urea
(organic compound) was first observed by Wohler who was a student of J.J.
Berzelius in Germany. Then, Berzelius was interested in a case in which two
clearly different materials had the same elemental composition and he
invested the term isomerism to describe it.
NH4OCN
ammonium cyanate
(CH4ON2)
NH2CONH2
urea
(CH4ON2)
Isomerism: is said to occur when two or more compounds have the same
molecular formula but different physical properties and/or chemical
properties. The compounds that exhibit this behavior are called Isomers.
There are two main types of isomerism: (i) structural (ii) stereoisomerism.
19
ISOMERISM
STRUCTURAL
POSITION
STREREOISOMERISM
FUNCTIONAL
GROUP
CHAIN
GEOMETRICAL
OPTICAL
butan-1-ol
OH
OH
(C4H10O)
butan-2-ol (C4H10O)
(ii)
H
OCH3
H
OCH3
1-methoxybutane (C5H12O)
2-methoxybutane
(C5H12O)
(ii). Functional Group Isomerism: This occurs when two or more isomers
have the same molecular formula but different functional groups, e.g. alcohol
and ether.
20
CH3CH2OH
and
ethanol (-OH)
CH3OCH3
dimethylether (-O-)
and
propanal
CH3COCH3
propanone(acetone)
O
F.G.
F.G.
CH3
(ii). Chain Isomerism: This occurs when two or more isomers have their
chains differently arranged. It occurs within the same homologous series.
There is an occurrence of straight and branched chain isomers. However, the
straight chain isomers have higher boiling point and lower volatility than the
branched chain counterparts despite they have the same molecular formula
e.g.
(i)
H
n-pentane (C5H12)
CH3
H
CH3 H
2-methylbutane (C5H12)
H
H
H C
H
CH3
CH3
2,2-dimethylpropane (C5H12)
CH3
C
CH3
H3C
transbut-2-ene
(opp. side of plane)
C
H
H3C
C
D
no geometrical isomerism
cis-but-2-ene
(same side of plane)
Cl
Cl
trans-1,2-dichloroethene
(opp. side of plane)
C
H
Cl
C
Cl
cis-1,2-dichloroethene
(same side of plane)
22
(i)
C2H5
OH
C2H5
HO
Cl
Cl
(ii)
COOH
COOH
C
H
C
OH
CH3
HO
CH3
23
24