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CHEMISTRY
CHEMISTRY
CHEMISTRY
CHEMISTRY SK016
Chapter
1.0
2.0
3.0
4.0
5.0
6.0
7.0
08/16/11
Topics
Hours
Matter
Atomic Structure
Periodic Table
Chemical Bonding
State of Matter
Chemical Equilibrium
Ionic Equilibria
Total
7
7
4
2
7
5
12
54
matter
CHEMISTRY SK026
Chapter
Topic
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
Thermochemistry
Electrochemistry
Reaction Kinetics
Intro To Organic Chemistry
Hydrocarbons
Aromatic Compounds
Haloalkanes (Alkyl halides)
Hydroxy compounds
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matter
Hours
4
6
7
4
8
3
4
3
3
CHEMISTRY SK026
Chapter
16.0
17.0
18.0
19.0
20.0
08/16/11
Topic
Carbonyl
Carboxylic acids & Derivatives
Amines
Amino acids and Proteins
Polymers
matter
Hour
4
4
5
2
1
ASSESSMENT
1. COURSEWORK (20%)
Practical work
- 10%
2. MID-SEMESTER EXAMINATION
- 10%
matter
REFERENCE BOOKS
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matter
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matter
Chapter 1 : MATTER
1.1 Atoms and Molecules
1.2 Mole Concept
1.3 Stoichiometry
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matter
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matter
Learning Outcome
At the end of this topic, students should be
able to:
(a) Describe proton, electron and neutron in
terms of the relative mass and relative
charge.
(b) Define proton number, Z, nucleon
number, A and isotope.
(c) Write isotope notation.
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matter
10
Introduction
Matter
Anything that occupies space and has
mass.
e.g: air, water, animals, trees, atoms, etc
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matter
11
Classifying Matter
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matter
12
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matter
13
SOLID
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LIQUID
matter
GAS
15
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matter
16
08/16/11
17
Subatomic Particles
Particle
Mass
Charge
Charge
(gram)
(Coulomb)
(units)
Electron (e)
9.1 x 10-28
-1.6 x 10-19
-1
Proton (p)
1.67 x 10-24
+1.6 x 10-19
+1
Neutron (n)
1.67 x 10-24
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matter
19
Isotope
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matter
20
Examples:
1
1
235
92
2
1
H (D)
238
92
3
1
H (T)
Isotope Notation
An atom can be represented by an isotope
notation ( atomic symbol )
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X=
Element symbol
Z =
A=
=
Nucleon number of X
p+n
matter
22
Nucleon number of
mercury, A = 202
Total charge on
the ion
Proton number
of mercury,
Z = 80
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matter
23
In a neutral atom:
number of protons equals number of
electrons
In a positive ion:
number of protons is more than number of
electrons
In a negative ion:
number of protons is less than number of
electrons
Exercise 1
Give the number of protons, neutrons, electrons
and charge in each of the following species:
Symbol
Number of :
Proton
200
80
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Neutron Electron
Hg
63
29
Cu
17
8
O 2
59
27
Charge
Co 3
matter
25
Exercise 2
Write the appropriate notation for each of the
following nuclide :
Species
A
B
C
D
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Number of :
Notation
Proton
Neutron Electron for nuclide
2
1
1
7
2
2
1
7
matter
2
0
1
10
26
b) Molecules
A molecule consists of a small number of
atoms joined together by bonds.
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matter
27
A diatomic molecule
Contains only two atoms
Ex : H2, N2, O2, Br2, HCl, CO
A polyatomic molecule
Contains more than two atoms
Ex : O3, H2O, NH3, CH4
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matter
28
Learning Outcomes
At the end of this topic, student should be able
to :
(a) Define relative atomic mass, Ar and
relative molecular mass, Mr based on
the C-12 scale.
(b) Calculate the average atomic mass of an
element given the relative abundance of
isotopes or a mass spectrum.
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matter
29
Relative Mass
i.
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matter
30
08/16/11
31
Example 1
Determine the relative atomic mass of an
element Y if the ratio of the atomic mass of Y to
carbon-12 atom is 0.45
ANSWER:
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matter
32
08/16/11
1
12
molecular
mass, Mr
Mass of one molecule
x Mass of one atom of
matter
12
33
Example 2
Calculate the relative molecular mass of
C5H5N,
Ar C = 12.01
Ar H = 1.01
Ar N = 14.01
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matter
35
MASS SPECTROMETER
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36
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matter
37
Modern mass
spectrum converts
the abundance into
percent abundance
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38
Relative abundance
63
8.1 9.1
24
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25 26
m/e
(amu)
matter
24Mg
39
Learning Outcomes
At the end of this topic, student should be able
to :
(a) Calculate the average atomic mass of an
element given the relative abundances of
isotopes or a mass spectrum.
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matter
40
Averageatomicmass
abundance
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matter
41
Example 1:
Calculate the relative atomic mass of neon
from the mass spectrum.
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42
Solution:
Average atomic
mass of Ne
=
= 20.2 u
Relative atomic mass Ne = 20.2
Example 2:
Copper occurs naturally as mixture of
69.09% of 63Cu and 30.91% of 65Cu. The
isotopic masses of 63Cu and 65Cu are 62.93
u and 64.93 u respectively. Calculate the
relative atomic mass of copper.
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44
Solution:
Average atomic
mass of Cu
=
=
(%abundance isotopicmass)
=
% abundance
63.55 u
Example 3:
Naturally occurring iridium, Ir is composed
of two isotopes, 191Ir and 193Ir in the ratio of
5:8. The relative isotopic mass of 191Ir and
193Ir are 191.021 u and 193.025 u
respectively. Calculate the relative atomic
mass of Iridium
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46
Solution:
mass of Ir
=
=
192.254 u
47
35Cl-35Cl
35Cl-37Cl
MASS SPECTROMETER
37Cl-37Cl
Cl2
35Cl-35Cl+
Cl2 + e
Cl2+
+ 2e
Cl2 + e 2Cl+ + 2e
35Cl-37Cl+
37Cl-37Cl+
35Cl+
37Cl+
Exercise:
How many peaks would be expected in a mass
spectrum of X2 which consists of 3 isotopes?
MATTER
1.2 Mole Concept
Learning Outcome
At the end of this topic, students should be
able to:
Avogadros Number, NA
Example:
1 mol of Cu contains 6.02 1023
Cu atoms
12.01 g
Mass of 1 C atom =
6.02 x 10 23
= 1.995 x 10-23 g
= 1.66 x 10-23 g
Example:
From the periodic table, Ar of nitrogen, N is 14.01
The mass of 1 N atom =
14.01 amu
14.01 g
14.01 g mol1
Mr of CH4 is 16.05
The mass of 1 CH4 molecule =
16.05 amu
Learning Outcome
At the end of this topic, students should be
able to:
(a) Interconvert between moles, mass,
number of particles, molar volume of gas
at STP and room temperature.
(b) Define the terms empirical & molecular
formulae
(c) Determine empirical and molecular
formulae from mass composition or
combustion data.
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MATTER
61
Example 1:
Calculate the number of moles of molecules for
3.011 x 1023 molecules of oxygen gas.
Solution:
6.02 x 1023 molecules of O2
3.011 x 1023
1 mol of O2 molecules
Example 2:
Calculate the number of moles of atoms for
1.204 x 1023 molecules of nitrogen gas.
Solution:
6.02 x 1023 molecules of N2
1.204 x
1023
1mol of N2 molecules
2 mol of N atoms
molecules of N2
23
1
.
204
10
molecules 2 mol
6.02 10 23 molecules
Example 3:
Calculate the mass of 0.25 mol of chlorine gas.
Solution:
1 mol Cl2
2 35.45 g
18 g
or
Example 4:
Calculate the mass of 7.528 x 1023 molecules of
methane, CH4
Solution:
6.02 x 1023 CH4 molecules (12.01 + 4(1.01)) g
7.528 x
1023
23
16
.
05
g
7.528
10
CH4 molecules
6.02 10 23
= 20.06 g
Temperature
273.15 K
0 C
and Pressure
1 atm
101325 N m-2
101325 Pa
760 mmHg
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MATTER
67
Example 1:
Calculate the volume occupied by 1.60 mol of
Cl2 gas at STP.
Solution:
At STP,
1 mol Cl2
occupies22.4 L
1.60 mol Cl2 occupies
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MATTER
69
Example 2:
Calculate the volume occupied by 19.61 g of
N2 at STP
Solution:
1 mol of N2
occupies
22.4 L
19.61 g
2(14.01) g mol 1
19.61
mol 22.4 L
2(14.01)
of N2 occupies
1 mol
= 15.7 L
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MATTER
70
Example 3:
0.50 mol methane, CH4 gas is kept in a cylinder at
STP. Calculate:
(a) The mass of the gas
(b) The volume of the cylinder
(c) The number of hydrogen atoms in the cylinder
Solution:
16.05
g
(a) Mass of 1 mol CH4
=
Mass of 0.50 mol CH4 16=.05 g 0.50 mol
1 mol
= 8.0 g
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MATTER
71
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MATTER
Exercise
A sample of CO2 has a volume of 56 cm3 at STP.
Calculate:
a) The number of moles of gas molecules
(0.0025 mol)
a) The number of CO2 molecules
(1.506 x 1021 molecules)
a) The number of oxygen atoms in the sample
(3.011x1021atoms)
Notes:
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1 dm3
1 dm3
= 1000 cm3
=1L
MATTER
73
MATTER
74
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MATTER
75
Example:
A sample of hydrocarbon contains 85.7%
carbon and 14.3% hydrogen by mass. Its
molar mass is 56. Determine the empirical
formula and molecular formula of the
compound.
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MATTER
76
Solution:
C
Mass
85.7
14.3
Number
of moles
85.7
12.01
14.3
1.01
Simplest ratio
= 7.1357
= 14.1584
1.984
2
56
n
14.03
3.99
4
Exercise:
A combustion of 0.202 g of an organic sample
that contains carbon, hydrogen and oxygen
produce 0.361g carbon dioxide and 0.147 g water.
If the relative molecular mass of the sample is
148, what is the molecular formula of the sample?
Answer : C6H12O4
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MATTER
79
Learning Outcome
At the end of this topic, students should be
able to:
(a) Define and perform calculation for each of
the following concentration measurements :
i) molarity (M)
ii) molality(m)
iii) mole fraction, X
iv) percentage by mass, % w/w
v) percentage by volume, %v/v
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MATTER
80
Concentration of Solutions
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MATTER
solvent
81
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MATTER
82
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MATTER
83
a) Molarity
Units of molarity:
mol L-1
mol dm-3
M
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MATTER
84
Example 1:
Determine the molarity of a solution
containing 29.22 g of sodium chloride, NaCl
in a 2.00 L solution.
Solution:
MNaCl
nNaCl
Vsolution
29.22
mol
(22.99 35.45)
2.00 L
0.250 mol L-1
Example 2:
How many grams of calcium chloride, CaCl2
should be used to prepare 250.00 mL
solution with a concentration of 0.500 M
Solution:
nCaCl M CaCl x Vsolution
2
= 13.9 g
b) Molality
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MATTER
89
Example:
What is the molality of a solution
prepared by dissolving 32.0 g of CaCl2 in
271 g of water?
Solution:
nCaCl 2
32.0 g
32.0 mol
Exercise:
Calculate the molality of a solution
prepared by dissolving 24.52 g of sulphuric
acid in 200.00 mL of distilled water.
(Density of water = 1 g mL-1)
Ans = 1.250 mol kg-1
nT
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MATTER
93
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MATTER
94
Example:
A sample of ethanol, C2H5OH contains
200.0 g of ethanol and 150.0 g of water.
Calculate the mole fraction of
(a) ethanol
(b) water
in the solution.
Solution:
nethanol
nwater
Xethanol
200.0 g
(2(12.01) 5(1.01) 16.00) g mol1
150.0 g
1
(2(1.01) 16.00) g mol
200.0 mol
45.07
45.07
18.02
0.3477
Xwater
= 1 0.3477
= 0.6523
mass
of
solute
%ww
x100
mass of solution
Note:
Mass of solution = mass of solute + mass of solvent
08/16/11
MATTER
98
Example:
A sample of 0.892 g of potassium
chloride, KCl is dissolved in 54.362 g of
water. What is the percent by mass of
KCl in the solution?
Solution:
0.892 g
% mass
100%
0.892 g 54.362 g
= 1.61%
Exercise:
A solution is made by dissolving 4.2 g of
sodium chloride, NaCl in 100.00 mL of
water. Calculate the mass percent of
sodium chloride in the solution.
Answer = 4.0%
%v
volume of solute
x 100
v volume of solution
Note:
mass of solution
Density of solution
volume of solution
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MATTER
101
Example 1:
25 mL of benzene is mixed with 125 mL
of acetone. Calculate the volume percent
of benzene solution.
Solution:
25 mL
% volume
100%
25 mL 125 mL
= 17%
Example 2:
A sample of 250.00 mL ethanol is labeled
as 35.5% (v/v) ethanol. How many
milliliters of ethanol does the solution
contain?
Solution:
Vethanol
% volume of ethanol
100 %
Vsolution
Vethanol
35.5% 250.00 mL
100%
88.8 mL
Example 3:
A 6.25 m of sodium hydroxide, NaOH
solution has has a density of 1.33 g mL-1
at 20 C. Calculate the concentration
NaOH in:
(a) molarity
(b) mole fraction
(c) percent by mass
Solution:
nNaOH
(a) M =
Vsolution
6.25 m of NaOH
there is 6.25 mol of NaOH in 1 kg of water
mass solution
=
solution
1250 g
1
1.33 g mL
MNaOH
6.25 mol
=
3
1250
10 L
1.33
= 6.65 mol L1
(b) XNaOH =
nNaOH
nNaOH n water
nwater
mass water
=
molar mass of water
1000 g
6.25 mol
1000
6
.
25
mol
mol
18.02
= 0.101
massNaOH
(c) %(w/w) of NaOH =
100%
massNaOH mass water
250 g
=
100%
250 g 1000 g
= 20.0%
Exercise:
An 8.00%(w/w) aqueous solution of
ammonia has a density of 0.9651 g mL-1.
Calculate the
(a)
molality
(b)
molarity
(c)
mole fraction
of the NH3 solution
Answer:
MATTER
1.3 Stoichiometry
Learning Outcome
At the end of the lesson, students should be able
to:
a) Determine the oxidation number of an
element in a chemical formula.
b) Write and balance :
i) Chemical equation by inspection method
ii) redox equation by ion-electron method
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MATTER
114
Example:
xA +
yB
zC +
Reactants
08/16/11
wD
Products
MATTER
115
08/16/11
MATTER
116
Inspection Method
1. Write down the unbalanced equation. Write the
correct formulae for the reactants and products.
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MATTER
117
Example:
Balance the chemical equation by applying the
inspection method.
NH3 + CuO Cu + N2 + H2O
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MATTER
118
Exercise
Balance the chemical equation below by applying
inspection method.
1. Fe(OH)3 + H2SO4 Fe2(SO4)3 + H2O
2. C6H6 + O2 CO2 + H2O
3. N2H4 + H2O2 HNO3 + H2O
4. ClO2 + H2O HClO3 + HCl
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MATTER
119
Redox Reaction
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MATTER
120
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MATTER
121
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MATTER
123
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MATTER
124
Exception:
1. H bonded to metal (e.g: NaH, MgH2) oxidation number
for H = -1
1. Halogen bonded to oxygen (e.g: Cl2O7)
number for halogen = +ve
oxidation
08/16/11
MATTER
125
Exercise
1.
1.
1.
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MATTER
126
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MATTER
127
MATTER
128
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i.
Fe2+ Fe3+
ii.
MnO4- Mn2+
MATTER
129
4H2O
MATTER
08/16/11
i.
ii.
MATTER
131
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MATTER
134
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MATTER
135
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MATTER
136
Exercise:
1.
2.
3.
4.
08/16/11
MATTER
137
Stoichiometry
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MATTER
138
Example 1:
How many grams of water are produced in the
oxidation of 0.125 mol of glucose?
C6H12O6(s) +
O2(g)
CO2(g) +
H2O(l)
Solution:
From the balanced equation;
1 mol C6H12O6 produce 6 mol H2O
0.125 mol
C6H12O6 produce
H2O
0.125 mol 6 mol
1 mol
Example 2:
Ethene, C2H4 burns in excess oxygen to form
carbon dioxide gas and water vapour.
(a) Write a balance equation of the
reaction
(b) If 20.0 dm3 of carbon dioxide gas is
produced in the reaction at STP, how
many grams of ethene are used?
Solution:
(a) C2H4 +
(b)
O2
CO2 +
H2O
20.0 dm 1 mol
20.0
22.4
CO2
20.0
mol
1 mol
22.4
2 mol
massethane
20.0
= 12.5 g
Learning Outcome
At the end of this topic, students should be
able to:
a)
Define the limiting reactant and
percentage yield
b)
Perfome stoichiometric calculations
using mole concept including limiting
reactant and percentage yield.
Limiting Reactant/Reagent
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MATTER
148
Example:
3H2 + N2 2NH3
If 6 moles of hydrogen is mixed with 6 moles of nitrogen,
how many moles of ammonia will be produced?
Solution:
3 mol H2 reacts with
1 mol N2
6 mol 1 mol
3 mol
= 2 mol N2
produce
6 mol H2 produce
2 mol NH3
6 mol 2 mol
3 mol
= 4 mol NH3
or
1 mol N2
6 mol N2
6 mol 3 mol
molNH3
1 mol
= 18 mol H2
H2 is not enough
limiting reactant
H2 limits the amount of products formed
3 mol H2
produce
6 mol N2
produce
2 mol NH3
= 4 mol NH3
Exercise:
Consider the reaction:
2 Al(s) + 3Cl2(g) 2 AlCl3(s)
A mixture of 2.75 moles of Al and 5.00 moles of Cl2 are
allowed to react.
(a) What is the limiting reactant?
(b) How many moles of AlCl3 are formed?
(c) How many moles of the reactant remain at
the end of the reaction?
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MATTER
154
PERCENTAGE YIELD
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MATTER
155
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MATTER
156
actual yield
% yield
x 100
theoretica l yield
08/16/11
MATTER
157
Example 1:
Benzene, C6H6 and bromine undergo reaction as follows:
C6H6 + Br2 C6H5Br + HBr
In an experiment, 15.0 g of benzene are mixed with excess
bromine
(a) Calculate the mass of bromobenzene, C6H5Br
that
would be produced in the reaction.
(b) What is the percent yield if only 28.5 g of
bromobenzene obtain from the experiment?
CHAPTER 2
ATOMIC STRUCTURE
Learning Outcomes
At the end of this topic students should be able
to:a) Describe the Bohrs atomic model.
b) Explain the existence of electron energy
levels in an atom.
c) Calculate the energy
of electron at 18
its level
1
E n= R H
(orbit) using.
, R H = 2.18x10
Learning Outcomes
d) Describe the formation of line spectrum of
hydrogen atom.
e) Calculate the energy change of an electron
1 1
RH
2
duringE =transition.
2
n1 n2
f)
where RH = 2.18 10
18
Learning Outcomes
g) Perform calculation involving the Rydberg
equation for Lyman, Balmer, Paschen,
1
1 Pfund
1
7
1
Brackett
and
series:
= RH
where
R
=
1.097
10
m
H
2
2
n1
n2
n1 n2
Learning Outcomes
i)
j)
1
En= RH 2
n
RH (Rydberg constant) = 2.18 x 10-18J.
n (principal quantum number) = 1, 2, 3 . (integer)
Note:
n identifies the orbit of electron
Energy is zero if electron is located infinitely far from
nucleus
n =1
E= Ef E i
Where:
Ef = RH
1
2
nf
1
1
E = R H 2 R H 2
n
n
f
i
E i= R H
1
2
ni
1
1
Thus, E = R H 2 2
n
n
f
i
E = hv
Where : h (Planck's constant) = 6.63 x 10-34 J s
v = frequency (s-1)
c
=
v
Where : c (speed of light) = 3.00 x 108 ms-1
Thus :
E =
hc
Rydberg Equation
Wavelength emitted by the transition of
electron between two energy levels is
calculated using Rydberg equation:
= RH
1
1
2
2
n1 n2
where R H = 1.097 10 m
n1 n2
Example 1
Calculate the wavelength, in nanometers of the
spectrum of hydrogen corresponding to n = 2
and n = 4 in the Rydberg equation.
Exercises:
1.
2.
Emission Spectra
Emission Spectra
Continuous
Spectra
Line
Spectra
Continuous Spectrum
A spectrum consists of radiation distributed over
all wavelength without any blank spot.
Example : electromagnetic spectrum, rainbow
It is produced by white light (sunlight or
incandescent lamp) that passed through a
prism
Line Spectrum
A spectrum that contain
only specific
wavelengths.
A spectrum of discrete
lines with certain
wavelengths.
Example: Emission
spectrum an element.
n=3
n=2
n=1
Emission of photon
Line
spectrum
Lyman Series
n=3
n=2
n=1
Emission of photon
Line
spectrum
Lyman Series
Balmer Series
Example
Complete the following table
Spectrum
region
Series
nf
ni
Lyman
2,3,4,
ultraviolet
Balmer
3,4,5,
Visible/uv
Paschen
4,5,6,
Infrared
Brackett
5,6,7,
Infrared
Pfund
6,7,8,
Infrared
Example
The following diagram is the line spectrum of
hydrogen atom. Line A is the first line of the
Lyman series.
A
C D E
Line
spectrum
Example
The line spectrum of Balmer is given as below:
W
Example
E
C B A
Line
spectrum
(a)
Paschen series
(b)
Solution
Line A.
The electron moves from n=4 to
n=3.
Example
With refer to the second line in the Balmer series of the
hydrogen spectrum, Calculate;
a)the wavelength in nm
b)the frequency
c)the energy
Example
Refer to last line of hydrogen spectrum in Lyman
series, Calculate:
a) Wavelength
b) Frequency
c) Wave number; where wave number =
For Lyman series; n1 = 1 & n2 =
Ans:
i.
9.116 x10-8 m
ii.
3.29 x1015 s-1
iii.
1.0970 X 107 m-1
Ionization Energy
Defination : Ionization energy is the minimum
energy required to remove an electron in its
ground state from an atom (or an ion) in
gaseous state.
M (g) M+ (g) + e
H = +ve
Ionization Energy
The hydrogen atom is ionised when electron is
removed from its ground state (n = 1) to n = .
At n = , the potential energy of electron is
zero, here the nucleus attractive force has no
effect on the electron (electron is free from
nucleus)
Example
n1 = 1, n2 =
E =
RH (1/n12 1/n22)
=
2.18 x 10-18 (1 0)
2.18 x 10-18 J
Ionisation energy
=
=
1312 kJ mol-1
Example
Calculate the energy to ionized :
(a) a hydrogen atom.
(b) 1 mol of hydrogen atom.
Solution
(a)
E= R H
1
1
2
2
n1 n2
1
1
2
2
1
18
= 2.18 10
18
2.18 10
Solution
(b) 1 H atoms need 2.18 x 1018 J
1 mol H atom
= 2.18 x 1018 x 6.02 x 1023
= 1.31 x 106 J
The energy to ionized 1 mol of hydrogen atom is
1.31 X 106 J
Example
10.97 10.66
10.52
10.27
9.74
8.22
Solution
E
= h X c/
= h x c x wave no.
de Broglies Postulate
In 1924 Louis de Broglie proposed that not only
light but all matter has a dual nature and
possesses both wave and particle properties.
Electron is both particle and wave.
Tiny particle such as electron does have wave
properties.
De Broglie deduced that the particle and wave
properties are related by the expression:
Example
Electron has dual nature properties. Why don't we
see the wave properties of a Baseball?
de Broglies Postulate
h
=
m
h = Planck constant (J s)
m = particle mass (kg)
= velocity (m/s)
= wavelength of a matter wave
x
where
h
p
4
mv
h = Planck constant
Learning Outcomes
At the end of this topic students should be able
to:Define the term orbital.
State the four quantum numbers in an orbitals.
sketch the 3-D shape of s, p and d orbitals.
Atomic Orbital
Definition
An orbital is a threedimensional region in
space around the
nucleus where there
is a high probability of
finding an electron.
Quantum Numbers
Each of the electrons in an atom is described and
characterised by a set of four quantum
numbers, namely
principal quantum number, n
angular momentum quantum number, l
magnetic quantum number, m
electron spin quantum number, s.
Orbital size
Energy
increases
three subshells
(s, p, and dorbitals)
1s
2s
3s
Shape of p orbital
px
py
pz
Shape of d orbital
dx2-y2
dxy
dz2
dxz
dyz
Exercise
Shell n
1
2
1
2
Orbital
notation
No. of orbitals
1s
2s
2p
-1,0,+1
Exercise
Predict the following quantum numbers whether
they are allowed or not
(a) (1,0,0,-)
(b) (2,0,1,1)
(c) (0,1,1,+)
(d) (4,1,0,-)
Learning Outcomes
At the end of this topic students should be able to:State and apply Aufbau principle, Hund's rule and
Pauli exclusion principle in filling of electrons in
orbitals of an atom.
Write the electronic configuration of atoms and
monoatomic ions.
(a) Orbital diagram
(b) spdf notation
Learning Outcomes
Explain the anomalous electronic configurations
of chromium and copper.
Introduction
The electronic configuration of an atom show
how electron are filled in the orbital.
Electronic configuration describes the
arrangement of electron in an atom.
Electronic Configuration
Method 1: Orbital diagram
Example: 8O
Box
1s
2s
2p
Electronic Configuration
Method 2: s,p,d,f notation
Example: 8O
2
1s
Principal quantum
number, n
2
2s
Number of electrons
in the subshells
4
2p
Azimuthal quantum
number, l
Electronic Configuration
To enable us to do electronic configuration, we
have to obey the following rules:
a) The Aufbau Principle
b) The Pauli Exclusion Principle
c) The Hund rule
Aufbau Principle
State that electrons are filled in the orbitals in
order of increasing energy.
Electrons should occupy the orbital with the
lowest energy first before enters the one with
higher energy.
5s
4p
3d
energy
Energy
n=4
4s
n=3
3p
3s
n=2
2p
2s
n=1
1s
(b)
10Ne
Hunds Rule
States that when electrons are added to the
orbital of equivalent energy (degenerate
orbitals), each orbital are filled singly with
electron of the same spin first before it is paired.
The electron in half-filled orbitals have the same
spins, that is, parallel spins.
Example
1) Carbon (6 electron)
1s
2s
2p
2) Oxygen (8 electron)
1s
2s
2p
Exercise
Write the electronic configuration of the following
atom or ion:
(a)C
(b)Ne
(c)Al
(d)Al3+
(e)Cl
(f)
Cl-
Element
Expected (Aufbau
Principle)
Observed/actual
Cr (Z=24)
1s22s22p63s23p6 4s2
3d4
Cu (Z=29)
1s22s22p63s23p6 3d9
4s2
1s22s22p63s23p6 3d10
4s1
Orbital diagram
24Cr
18[Ar]
3d
4s
Actual
18[Ar]
3d
4s
Cu :
18[Ar]
3d
4s
Cu :
18[Ar]
3d
2 2s2 2p6 3s2 3p6
Ar
:
1s
18
4s
LEARNING OUTCOMES
Transition metals
GROUP
Main Groups in Periodic Table
Group 1
Group 2
Group 3-11
Group 17
Group 18
Group 12
:
:
:
:
:
:
Blocks
All the elements in the Periodic Table can
be classified into 4 main blocks according
to their valence electrons configuration.
These main blocks are s, p, d and f block.
s- block
Group 1 and 2
The filling of valence electrons involve the s
orbital
Configuration of the valence electrons :
ns1 to ns2
Eg:
2 2s2 2p6 3s1
Na
:
1s
11
2 2s2 2p6 3s2 3p6 4s2
Ca
:
1s
20
9
p-block
Group 13 to 18
The filling of valence electrons involve s and
p orbital.
The configuration of valence electrons:
ns2 np1 to ns2 np6
Eg.
2 2s2 2p6 3s2 3p1
Al
:
1s
13
2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2
Te
:
1s
52
5p4
10
d-block
Groups 3 to 12
The filling of valence electrons involve s and d
orbitals.
Group 3 to 11 known as Transition metal.
Configuration of valence electron :
Eg.
(n-1) d1 ns2 to (n-1) d10 ns2
2
2
6
2
6
3
2 or
23V : 1s 2s 2p 3s 3p 3d 4s
[Ar] 3d3 4s2
where [Ar] = 18 electrons
11
f-block
Involve the elements in the series of
lanthanides (Ce to Lu) and actinides (Th
to Lr).
The filling of valence electrons happen in
the subshell of 4f and 5f.
12
elements
block
period
group
2 2s2
K
:
1s
19
2p6 3s2 3p6
2
1
Mg
:
1s
12 4s
2 2p62 3s22
2s
P
15 : 1s 2s
2p6 3s2 3p3
2 2s2
Bv
:
1s
35
2p6 3s2 3p6
2 2s52
2
10
Ni
:
1s
4s
4p
28 3d
2p6 3s2 3p6
2 3d
8 2 2s2
Zr
:
1s
4s
40
2p6 3s2 3p6
4s2 3d10 4p6
5s2 3d2
s
p
3
3
2
15
Numbe
r of
velenc
1
e
electro
2
n
5
17
10
10
Example
Element
Group
Period
Class/block
18
B
C
D
17
Block s
Transition element/
block d
Inert gas / block p
18
16
3.2 Periodicity
4.2.1 Periodic trends in the size of atom
(atomic radii)
The size /radius of atom is difficult to be
defined exactly because the electron cloud
has no clear boundary.
Therefore, the atomic radius is taken as
half of the distance between the nuclei of
two adjacent identical atom.
17
Radius, r = a/2 ()
Size
volume
V = 4/3 r3 , V r
21
23
Across
period 3
Across
Period 2
24
Example
Arrange the following atoms in order of increasing radius P,Si,N.
Solution
N and P are in the same group and N is above
P.
Atomic radius increases as we go down the
group.
Therefore, the radius of N is smaller than that
of P
Both Si and P are in the third period and Si is
to the left of P.
Atomic radius decreases as we move from
left to right.
Therefore, the radius of P is smaller than Si.
Thus the order of increasing radius :
Group
14
Group
15
N
Si
N<P<Si
26
27
29
Isoelectronic species
Isoelectronic species are groups of atoms and
ions which have the same electronic configuration.
Within isoelectronic species:
a) the more positive the charge, the smaller the
species
E.g :
Na+, Mg2+, Al3+and Si4+ ions are isoelectronic
(10 e) with the electron configurations as
1s2 2s2 2p6.
30
Exercise
Na+,Si4+ ,Mg2+, N3- ,O2- ,Al3+ and F- are
isoelectronic with the electronic configuration as
1s2 2s2 2p6. Arrange in an descending order
the size of those isoelectronic species.
Answer :
N3- > O2- > F- > Na+ > Mg2+ > Al3+> Si4+
33
34
35
Be
B
N
O
37
39
42
Example 1
4Be
The ionization energies (kJmol-1) of Beryllium
are shown below.
IE1
899
IE2
1757
IE3
14850
IE4
21005
43
1757
1.95
899
14850
8.45
1757
21005
1.41
14850
44
45
Example 2
Five successive ionization energies (kJmol-1)
of atom M is shown below:
IE1
800
IE2
1580
IE3
3230
IE4
IE5
4360 16000
Determine
i) the electron configuration of the valence
electron.
ii) the group number in the periodic table.
46
47
48
a) Across period
The nuclear charge increase
The atomic size decrease
Hence, the nucleus attraction stronger
Therefore, the electronegativity
increase
49
b) Down a group
50
51
Na
98
Mg Al
Si
P S
Cl
Ar
650 660 1410 44 120 -101 -189
52
53
Na+ Na+
Na+
e
Na+
Na+
Na+
e
Na+ Na+
Na+
e
Na+ Na+
Na+
54
55
56
Group 1
The size increase, the attraction between
nucleus and electron sea become weaker.
Therefore, less energy is needed to
overcome the attraction.
Thus, melting and boiling point
decrease.
57
Group 17
The size of molecules increase, the
intermolecular forces (Van der Waals) become
stronger.
Therefore, more energy is needed to overcome
the attraction
- Thus, melting and boiling point increase.
58
Metallic character
Metallic properties are:
- shiny with various colours and most are silvery.
- malleable and ductile
- good thermal and electric conductor
Generally, metallic character :
- Increases down a group
- Decreases across the period
59
metal
Metalloids
(semimetal)
nonmetal
60
Si
S Cl
acid
63
base
64
P:
P4 (s) + 3O2 (g) P4O6 (s)
P4O6 (s) + 6H2O (l) 4H3PO3 (aq)
phosphorus acid
65
S:
S (s) + O2 (g) SO2 (g)
SO2 (g) + H2O (l) H2SO3 (aq)
sulfurous acid
Cl :
Cl2O7 (g) + H2O (l) 2HClO4 (aq)
hypochloric acid
66
CHAPTER 4
CHEMICAL BONDING
CHAPTER 4
CHEMICAL BONDING
4.1 Lewis Structure
4.2 Molecular Shape and Polarity
4.3 Orbital Overlap and Hybridization
4.4 Intermolecular Forces
4.5 Metallic Bond
Lewis Symbol
Example
The Lewis symbol of atom
Group
13
14
15
16
17
18
Valence
electron
Lewis dot
symbol
4.1.2
Octet Rule
2)
4.1.3.1
Example 1: NaCl
Example 2: CaCl2
Ca: 1s2 2s2 2p6 3s2 3p6 4s2
(Has two electrons in its outer shell)
Cl: 1s2 2s2 2p6 3s2 3p5
(Has seven outer electrons)
Calcium Chloride
If Ca atom transfer 2 electrons, one to each
chlorine atom, it become a Ca2+ ion with the stable
configuration of noble gas.
Ionic bond
Example 3: LiF
+
1) CaCl2
+
2) MgO
+
3) CaBr2
Exercises:
Example
7e-
F F
7e-
8e- 8e-
Lewis structure of F2
single covalent bond
lone pairs
lone pairs
F F
lone pairs
9.4
Covalent compounds:
H + O+ H
H O H
2e- 8e- 2e-
or
single covalent bonds
O
8e-
8e-
8e-
double bonds
or O
double bonds
Triple
bond
two
atoms
share
+
three pairs of electrons
N
8e-
or
8e-
triple bond
triple bond
i.Single bond
i.Double bond
i.Triple bond
Example
Draw the Lewis structure for each of the
following compounds:
i. HF
ii. CH4
iii. CHCl3
iv. NH3
v. H2O
Number of electrons
C : 4e
4H: 4e
Total : 8e
Center atom: N
Count electrons:
C : 4e
H : 1e
3Cl: 21e
Total: 26 e
Count number of
electrons
N :
3H :
Total :
5e
3e
8e
1.54
1.34
C C
1.20
EXAMPLE
1) Draw all the possible Lewis structure
of COCl2.
2) Predict the most plausible structure.
SOLUTION
1)
2)
EXERCISE 1
EXERCISE 2
EXERCISE 3
1) HCN
1) CO2
1) SCN
Three conditions:
1) Incomplete octet
2) Expanded octet
3) Odd no. electron
EXERCISE:
Write Lewis structures of the
following compounds/ ions:
CCl4
CO32-
HCN
PCl3
HNO3
PO43-
C2H4
C2H2
CH2Cl2
ICl
NH4+
NF3
H2S
N2H4
PH3
CS2
NO2-
XeF4
NH3
HCOOH
SO42-
ICl4-
SF6
O3
NO2
LEARNING OUTCOMES
At the end of the lesson, students should
be able to;
1. Explain valence shell electron repulsion theory.
(VSEPR)
2. Draw the basic molecular shapes : linear, trigonal
planar, tetrahedral, trigonal bipyramidal and
octahedral.
3. Predict and explain the shapes of molecule and
bond angles in a given species.
4. Explain bond polarity and dipole moment.
5. Deduce the polarity of molecules based on the
shapes and the resultant dipole moment
63
64
VSEPR theory
5 basic shapes
polarity
Molecular shape:
Introduction
65
4.2.1 VSEPR
The Valence-Shell Electron Repulsion
theory states that:
The valence electron pairs around
the central atom are oriented as far
apart as possible to minimize the
repulsion between them.
66
69
A.
Example: BeCl2
Lewis structure
Be : 2e
180
2Cl :14e
Total : 16 e
..
..
Cl:
Cl Be
..
..
:
70
Linear
B.
Example: BCl3
Repulsive forces
Lewis structure
between pairs are the
B: 3e
same
3Cl : 21e
Total: 24e
:
120
..
..
Cl :
..
..
:
71
..
Cl
..
Cl
Trigonal planar
Equal repulsion
between bonding pairs
equal angle
H
H
109.5
Tetrahedral
72
90
..
..
..
..
Cl
73
..
Cl :
120
..
..
Cl :
..
..
Cl
..
Cl
Shape:
Trigonal bipyramidal
F
F
F
S
F
F
74
Octahedral
90o
90o
Number
of bonding
pairs
Number
of lone
pairs
AB2
Shape
180
Linear
75
Number
of bonding
pairs
Number
of lone
pairs
AB3
Shape
120
76
trigonal planar
Number
of bonding
pairs
Number
of lone
pairs
AB4
Shape
109.5o
77
Tetrahedral
Number
of bonding
pairs
Number
of lone
pairs
AB5
Shape
90
120
78
Trigonal pyramidal
Number
of bonding
pairs
Number
of lone
pairs
AB6
Shape
90
90
79
Octahedral
81
82
83
84
85
86
87
88
89
90
Number
of bonding
pairs
Number
of lone
pairs
AB2E
Shape
Bent / V-shaped
91
92
Class of
molecules
Number
of bonding
pairs
Number
of lone
pairs
AB3E
Shape
Trigonal pyramidal
Bond angle : < 109.5o
Number
of bonding
pairs
Number
of lone
pairs
AB2E2
Shape
Bent / V-shaped
Bond angle : < 109.5o
93
94
Class of
molecules
Number
of bonding
pairs
Number
of lone
pairs
AB4E
Shape
Distorted tetrahedral
(see-saw)
Bond angle : < 90o
95
Class of
molecules
Number
of bonding
pairs
Number
of lone
pairs
AB3E2
Shape
T-shaped
Bond angle : < 90o
96
Class of
molecules
Number
of bonding
pairs
Number
of lone
pairs
AB2E3
Shape
Linear
Bond angle : 180o
97
Class of
molecules
Number
of bonding
pairs
Number
of lone
pairs
AB5E
Shape
Square pyramidal
Bond angle :90o and
180o
98
Class of
molecules
Number
of bonding
pairs
Number
of lone
pairs
AB4E2
Shape
Square planar
Bond angle : 90o
99
109.5o
100
107.3o
104.5o
a) CH4
Has 4 bonding pairs electrons.
The repulsion between the bonding pairs
electrons are equal.
equal
The bond angles are all 109.5o
101
b) NH3
c) H2O
= Qr
E.g : Polarity of HF
Hydrogen fluoride is a covalent molecule with
a polar bond.
F atom is more electronegative than H atom,
so the electron density will shift from H to
F.
The symbol of the shifted electron can be
represented by a crossed arrow to indicate
the direction of the shift.
H
105
106
107
108
Example
Predict the polarity of the following molecules:
109
110
111
( c) Chloromethane, CH3Cl
(d ) Ammonia, NH3
114
BOND
NON-POLAR
POLAR
NON-POLAR
MOLECULES
NON-POLAR
MOLECULES
Symetrical molecules
- basic molecular shape with the
same terminal atom
- molecules with lone pairs linear
(from trigonal bipyramidal) and
square planar with the same
terminal atom
115
POLAR
MOLECULES
Non-symetrical molecules
- basic molecules with different
terminal atom
- molecules with lone pairs except
linear and square planar
Exercises :
Predict the polarity of the following molecules:
116
Objectives
At the end of this subtopic, students should be
able to:
1. Draw and describe the formation of sigma(
and pi() bonds from overlapping of orbitals.
2. Draw and explain the formation of hybrid
orbitals of a central atom: sp, sp2, sp3, sp3d, sp3d2
using appropriate examples.
3. Draw orbitals overlap and label sigma( and
pi() bonds of a molecule.
118
4.3.1
Example:
H
Change in electron
density as two hydrogen
atoms approach each
other.
High electron density as
the orbitals overlap
(covalent bond formed)
120
10.3
a) sigma bond ()
b) pi bond ()
121
a) bond
formed when orbitals overlap along its
internuclear axis (end to end overlapping)
Example:
i. overlapping s orbitals
bond
122
ii.
Px orbital
H
bond
123
bond
124
b) bond
Formed when two p-orbitals of the same
orientation overlap sideways
y
125
bond
bond
126
127
128
O2
Consider the ground state configuration:
O : 1s2 2s2 2p4
y
1s
2s
2p
129
130
N2
131
4.3.2
Hybridization of orbitals:
mixing of two or more atomic orbitals to form a new
set of hybrid orbitals
132
Hybridization
Hybrid orbitals have different shapes
from original atomic orbitals
Types of hybridisation reflects the
shape/geometry of a molecule
Only the central atoms will be involved
in hybridisation
133
10.4
Hybridization of orbitals
i. sp
ii. sp2
iii. sp3
iv. sp3d
v. sp3d2
134
sp3 hybridization
one s orbital and three p orbitals are mixed to
form four sp3 hybrid orbitals
the geometry of the four hybrid orbitals is
tetrahedral with the angle of 109.5o .
135
sp3 hybrid
Mixing of s and three p orbitals
sp3
sp3
sp3
sp 3
136
Example:
1)
CH4
Lewis structure :
Valence orbital diagram ;
H:
C ground state :
C excited :
C hybrid :
Orbital Overlap :
Molecular Geometry :
137
2s
Lewis Structure
H
H C H
H
2p
Excitation: to have 4
unpaired electrons
H
sp3
Excited state :
1s
2s
2p
C
sp3
sp3 hybrid
shape: tetrahedral
138
sp3
sp3
H
Fig. 10.8
sp3
1s
sp3
sp3
sp3
1s
139
1s
Example 2 :
NH3
Lewis structure :
Valence orbital diagram ;
H:
N ground state :
N excited :
N hybrid :
Orbital Overlap :
Molecular Geometry :
140
Fig. 10.9
sp3
1s
sp3
sp3
sp3
1s
141
1s
Example:
3) H2O
Lewis structure
142
2
sp
hybridization
143
Fig. 10.12
px
sp2
py
144
one
s orbital + two p orbitals
sp2
sp2
Shown together
(large lobes only)
145
Example:
1) BF3
Lewis structure
Example: BF3
Pure p orbital
sp2
sp2
F : 1s22s22p5
sp2
147
Example:
2) C2H4
Lewis structure
148
Fig. 10.16a-c
bonds
bond
149
150
10.5
sp hybridization
one s orbital and one p orbital are
mixed to form two sp hybrid orbitals
the geometry of the two hybrid
orbitals is linear with the angle of
180o
151
sp
sp
152
10.4
Example:
1) BeCl2
Lewis structure
Fig. 10.11
154
Example:
2) C2H2
Lewis structure
155
Fig. 10.19a-c
156
Example:
3) CO2
Lewis structure
3
sp d
hybridization
158
159
Example:
1) PCl5
Lewis structure
Example:
2) ClF3
Lewis structure
3
2
sp d
hybridization
162
163
Example:
1) SF6
Lewis structure
Example:
2) ICl5
Lewis structure
Hybridization
Examples
sp
BeCl2
sp2
BF3
sp3
sp3d
PCl5
sp3d2
SF6
166
10.4
167
Exercise:
For each of the following, draw the orbital
overlap to show the formation of covalent
bond
a) XeF2
b) O3
c) ICl4
d) OF2
168
LEARNING OUTCOMES
At the end of the lesson, students should be able
to;
1.
2.
3.
1.
Types of intermolecular
forces
4.4.2The effect of
intermolecular
forces
on
the
physical
properties.
171
Intermolecular Forces
172
Effects of intermolecular
forces on physical properties
Intermolecular Forces
Van der Waal
Forces
Hydrogen
Bond
Between
covalent
molecules
Between
covalent
molecules
with H
covalently
bonded to
F, O or N
174
4.4.1.1
175
Dipole-dipole forces
(permanent dipole forces)
Exist in polar covalent compounds
Polar molecules have permanent dipole due
to the uneven electron distributions
Example:
Cl
Chlorine is more
electronegative,
thus it has higher
electron density
Cl
176
178
Example:
London forces in Br2
Electrons in a molecule
move randomly about the
nucleus
Br
Br
Temporary
dipole molecule
Br
Br
Br
Br
London forces
179
180
Hydrogen
intermolecular bond
181
Other examples:
NH3 liquid
H2O
..
H
Hydrogen
intermolecular bond
..
N
..
H
H
H
..
..
..
..
Hydrogen
intermolecular bond
Covalent bond
..
..
..
H
Hydrogen
intermolecular bond
182
Hydrogen bond
..
..
H
O
O
..
O
..
in
Not a hydrogen
bond
..
..
H
H
H is not
bonded to
either F, O
or N
C
H
H
H
183
Example: H2O
H
O H
H
O H
O H
H
O H
184
185
Boiling point
Solubility
A. Dissolve in polar solvent
The molecules that posses
Hydrogen bonds are highly polar.
They may form interaction with
any polar molecules that act as
solvent.
B. Dissolve in any solvent that can
form Hydrogen bonds
187
Example
NH3 dissolves in water because it can form
Hydrogen intermolecular bond with water.
..
..
Hydrogen bond
..
..
N
H
H
H
H
H
188
Problem:
HI
HBr
HCl
Molecular mass
189
Answer
Density
Ice (solid H2O) has lower density
compared to its liquid. Refer to the
structure of ice
193
194
195
196
Fig. 11.13
197
Answer:
199
200
201
202
203
204
Vapour Pressure
in a closed system :
Fig. 11.34
In a close system .
Liquid molecules vapourise
Fig. 11.35
Boiling Point:
the temperature at
which the vapour pressure of a liquid is
equal to the external atmospheric
pressure.
Intermolecular forces
LEARNING OUTCOMES
At the end of the lesson, students should be
able to;
1.
2.
3.
4.
Metallic bond
An electrostatic force between
positive charge metallic ions and the
sea of electrons.
Bonding electrons are delocalized
over the entire crystal which can be
imagined as an array of the ions
immersed in a sea of delocalized
valence electron.
217
Metallic bonds
Positive
ions are
immersed in
the sea of
electrons
Free
moving
electrons
e
218
+ e + e
220
221
Na
+1
+1
e
e
+1
e
+1
+1
e
e
+1
+1
+1
e
e
+1 +1
+1
e
+1
+1
e
+1
+1
e
e
e
+1 +1 +1
ee ee ee ee ee
+2 +2 +2 +2 +2
ee ee ee ee ee
+2 +2 +2 +2 +2
ee ee ee ee ee
ee
+2 +2 +2 +2 +2
ee ee ee
+2 +2 +2
ee ee ee
+2 +2 +2
ee ee ee
+2 +2 +2
Example:
Explain the difference in the
boiling point of the two metals
given:
Magnesium 11300 oC
Aluminum 24500 oC
223
Answer
225
CHAPTER 5.0
STATES OF MATTER
5.1
5.2
5.3
Gas
Liquid
Solid
Partial pressure
Dalton's law
(j) perform calculation using Dalton's law
(k) compare the ideal and non-ideal behaviours of gases in terms
of intermolecular forces and molecular volume
(l) explain the conditions at which real gases approach
the ideal behaviour.
(m) explain qualitatively van der Waals equation and relate the
values of a and b to intermolecular forces and molecular volume
of a gas
General
Properties
of Gas
Particles of gas are far apart and fill the available space.
V P
PV = k
Graph of P versus 1
Graph of P versus V
P
P
1
V
pressure is inversely
proportional to volume
pressure is directly
1
proportional to
volume
Graph of PV versus P
PV
PV = constant
Example 1
A sample of chlorine gas occupies a volume of 2 L at a pressure
of 1 atm. Calculate the pressure of the gas if the volume is
increased to 5 L at constant temperature.
0.4 atm
Example 2
The pressure of a sample of hydrogen gas in a 50.0 mL container is
765 mmHg. The sample is then transferred into another container and
the measured pressure is 825 mmHg. What is the volume of the second
container?
46.36 mL
a) Charless Law :
The volume of a fixed amount of gas at
constant pressure is directly proportional to the
absolute temperature of the gas (in Kelvin).
V T (no of mole and pressure constant)
V
=k
T
Where :
k = constant
T = absolute temperature (K)
V = volume
V1 V2
T1 T2
Where V1 = initial volume
T1 = initial temperature
V2 = final volume
T2 = final temperature
T = absolute temperature
in Kelvin (K)
T(K) = TC + 273.15
T(K)
-273.15
T(0C)
Example 1
A sample of carbon monoxide gas occupies 3.2 L
At 125 C. The sample is then cooled at constant
pressure until it contracts to 1.54 L. Calculate the
final temperature in degree Celsius.
-81.54 C
Example 2
A sample of gas trapped in a capillary tube by a
plug of mercury at 22 oC has a volume of 4.5 mL.
Calculate the volume of the gas when the capillary
tube is heated to 60 oC.
5.08 mL
T
P
T
V= k
P
PV
=k
T
V
P1V1
T1
P2V2
T2
Example 1
Ans : 35.32 L
Example 2
2 moles of chlorine gas kept in a cylinder with
piston occupies a volume of 49 L. When another 3
moles of chlorine gas is pumped into the cylinder
at constant temperature and pressure the piston
moves
upwards
to
accommodate
the
gas.
C) Avogadros Law
At constant pressure and temperature,
temperature the volume of a
gas is directly proportional to the number of moles of the
gas present
V n (P and T are constant)
V = k n
V
=k
n
V1 V2
n1 n2
where :
n = number of moles
k= constant
Avogadro's Law:
V
V=R
Vn
nT
P
nT
P
PV = nRT
Ideal gas equation
Where :
R = gas constant
T = Temperature(K)
n = number of moles
V = volume
P = Pressure
Pa
unit of
volume
value of
R
unit of R
8.314
Nm mol1 K1
J mol1 K1
Example 1
Example 2
the
Ideal
Gas
PV nRT
m
PV=
RT
Mr
mRT
Mr =
PV
m
where: n =
Mr
Mr = molar mass of a gas
Density of a gas
PV nRT
m
PV= RT
Mr
mRT
P=
VM r
dRT
P=
Mr
PM r
d=
RT
where,
d = density of a
gas
Example
1
Calculate the density of ammonia (NH3) in grams
per litre (g/L) at 752 mmHg and 55 C.
Ans : 0.625 gL-1
Example 2
A chemist has synthesized a greenish-yellow compound of
chlorine and oxygen and finds that its density is 7.71 g L-1
at 36 C and 2.88 atm. Calculate the molar mass of the
compound.
Example 3
Ans : 8.0 g
nA RT
pressure exerted by gas A = PA =
V
nBRT
=
V
=
V
V
= (nA + nB )RT
V
when nA + nB = nT
n TRT
PT =
V
Ptotal ntotal(RT )
Thus:
PA
n A ( RT )
Ptotal ntotal ( RT )
PA X A Ptotal
PA
nA
PTotal
nTotal
Example
1
A gaseous mixture of 7.00 g N2 and 3.21 g CH4 is placed in
a 12.0 L cylinder at 25 oC.
Example 2
A mixture of gases contains 4.53 moles of neon, 0.82
moles of argon and 2.25 moles of xenon. Calculate the
partial pressure of the gases if the total pressure is 2.15 atm
at a certain temperature.
atm, P
Xe = 0.63 atm,
Example 3
A sample of gas at 5.88 atm contains 1.2 g CH4, 0.4 g H2 and
0.1 g He. Calculate :
a)
b)
gas
The gas collected is actually a mixture of the gas and water vapour.
PT Pgas PH 2O
Vapour pressure of water, Pwater = 23.8 torr
Example 1
Consider the reaction below :
2KClO3
2KCl + 3O2
Example 2
Excess amount of hydrochloric acid is added to 2.5 g of pure
zinc. The gas produced is collected over water in a gas cylinder
at 28 oC and 100.0 kNm-2. Calculate :
Ideal gas
any gas that obeys the ideal gas
equation and has the properties as
outlined by the Kinetic Molecular
Theory
Reason:
At low pressure:
To achieve a low pressure, the volume of
a container is increased.
Thus, the molecules will be far apart from
another, hence the intermolecular forces
can be neglected.
At a low pressure the size of a container is
extremely large compared to the size of
molecules, thus the size of molecules can
be neglected.
Reason :
At low pressure
At low pressure, the volume of a container
is very large
Thus the molecules will be more far apart
from one another. Hence the
intermolecular forces can be neglected.
At low pressure, the volume of the
container is extremely large compared to
the size of the molecules, thus the volume
can be neglected
At high temperature
The gas molecules have high kinetic
energies and move at high speed
The molecules are able to free themselves
from the intermolecular forces that act
between them.
The intermolecular forces can be
neglected, thus they behave almost
ideally.
RT
600K
1000K
The lines
approach the
ideal line when
T increases
n=number of moles
V = volume
V = Vcontainer - nb
n = number of moles
b = size factor
& V = V container - nb
Value of a :
a is a positive constant which depends on the
strength of the attractive forces between molecules
Molecules with a higher value of a have stronger
attractive forces.
Value of b :
b is a constant to represent the volume occupied
by the molecules.
Larger molecules have bigger value of b
5.2 Liquids
2. Surface tension
Fig. 11.8
molecule at
the surface
molecule within
the liquid
3. Viscosity
4. Compressibility
5. Diffusion
Vaporisation Process
i) Surface area
ii) Temperature
~ temperature , the kinetic energy
more molecules have enough energy to
Condensation Process
Vapour Pressure
molecules escape from the surface of a liquid
: referred as vapour molecules
Pressure exerted by the vapour molecules
on the surface of a liquid is known as the
vapour pressure
in a closed system :
Boiling
A process in which liquid molecules
change to vapour at a particular
temperature and at an atmospheric
pressure.
Happens throughout the liquid.
Evaporation
liquid molecules change to vapour at
any temperature and pressure.
Occurs only at the surface of a liquid
Boiling Point:
the temperature at
which the vapour pressure of a liquid is
equal to the external atmospheric
pressure.
Normal Boiling Point: the temperature
at which a liquid boils when the external
pressure is 1 atm (that is the vapour
pressure is 760 mmHg)
5.3 Solid
OBJECTIVE
(a) State the properties of solid.
(b) Explain the process of:
- freezing
- sublimation
- melting
- deposition
ii. ionic
Properties of solid
1.Particles are closely arranged and regularly in order
2. Rigid arrangement- particles can vibrate, rotate
about fixed position and cannot move freely without
disrupting the whole structure.
3. Has definite shape and volume.
4.Has strong forces between the particles.
5. Has high densities.
6. Incompressible.
7.Diffusion within the solid is extremely slow.
liquid
sublimation
deposition
solid
gas
Sublimation Process
The process by which a substance changes
directly from solid to the gaseous state without
passing through the liquid state.
Occurs on solid with weak intermolecular forces
of attraction
Deposition Process
The process where molecules from vapour state
change to the solid state.
The opposite process of sublimation
Types of Solid
crystalline solid
A solid that has highly ordered
amorphous solid
Solid that does not have a
arrangement of atoms or
molecules
arrangement
Formed when a saturated
2.
Ionic solids
forces
(van
der
Waals
4.
covalent bond
examples : diamond, graphite, SiO2
5.4 Phase
Diagram
Learning Outcomes :
At the end of this lesson students should be able to:
(a)
Define phase .
(b)
(c)
(d)
(e)
(i)
T
A
8/16/11
8/16/11
Important Points
1. Point T :
- Known as the triple point
- Triple point is the point at which the vapour, liquid and
solid states of a substance are in equilibrium.
- Triple point for water is 0.01C and 0.06 atm.
2. Point C :
- Known as the critical point
- Critical point is the point on a phase diagram at which
the vapour cannot be condensed to a liquid.
- The liquid gas line ends at the critical point.
- Above the critical point, the liquid cannot be
distinguished from its vapour form.
8/16/11
(ii)
8/16/11
TRIPLE POINT
At point T, the triple point; solid, liquid and
vapour are in equilibrium
CO2(s) CO2(l) CO2(g)
8/16/11
Exercise:
a) Describe the phase change when carbon
dioxide undergoes isobaric heating at 5.2 atm
pressure
Exercises:
b) Describe the phase change when pressure is
applied to water isothermally at 0.01 C
Chemical Equilibrium
Chapter 6
AgCl + NO3
6.1.2
Reversible Reaction
Example 2
H2(g) + I2(g)
2HI(g)
H2O (g)
concentration
[N2O4] at equilibrium
time
cC (g) + dD (g)
[C]c[D]d
[A]a[B]b
Table 6.1
N2O4 (g)
K=
[NO2]2
[N2O4]
2NO2 (g)
= 4.63 x 10-3
constant
Kc=
Example 6
CH3COOH (aq) CH3COO- (aq) + H+ (aq)
Kc=
(PA)a (PB)b
Example 7
Write the equilibrium law in the form of Kp
and Kc for the following reactions:
a) N2(g) + 3H2(g) NH3(g)
b) 2NO(g) + O2(g) N2O4(g)
Answer:
Kp =
Kc =
Expression of Kc
Expression of Kc depends on the equilibrium
equation given
Example 8
2SO3 (g) 2SO2 (g) + O2 (g)
Kc = [SO2]2 [O2]
[SO3]2
Kc2 =
[SO3]2
[SO2]2 [O2]
Example 9
Find the relationship between Kc1 and Kc2 for the
following equilibrium equations.
1. SO3 (g) SO2 (g) + O2 (g)
Kc2 =
[SO3]2
[SO2]2 [O2]
Example 10
Consider the following reaction:
A(g) + B(g) 2C(g)
If 5 moles of A are allowed to mix and react
with 3 moles of B in 1dm3 container, 2 moles
of C are produced at equilibrium. What is the
value of Kc for this reaction?
(Ans: 0.5 )
Example 11
Consider the reaction:
CO(g) + 2H2(g) CH3OH(g)
The following equilibrium concentrations are
achieved at 400K:
[CO]
= 1.03M
[H2]
= 0.332M
[CH3OH] = 1.56M
Determine the equilibrium constant at 400K
(Ans: 13.74 M-2)
Example 12
Nitrogen gas reacts with oxygen gas at high
temperature to form nitrogen monoxide gas,
NO. The equilibrium constant for the reaction is
4.1 x 10-4 at 200oC.
If the concentration for both N2(g) and O2(g) at
equilibrium are 0.40 moldm-3 and 1.3 moldm-3
respectively, calculate the concentration of NO
gas at equilibrium?
(Ans: 0.0146 M)
Example 13
The equilibrium constant Kp for the reaction;
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure
of O2 if the P NO2 = 0.400 atm and PNO = 0.270
atm?
Answer;
2
PNO
PO
Kp =
PO =
2
2
PNO
2
2
PNO
2
Kp
2
PNO
cC (g) + dD (g)
[C]c[D]d
[A]a[B]b
Thus,
Kc =
Since P = nRT
V
[ ]=
P
RT
cC (g) + dD (g)
Kc = Kp (RT) (a + b) (c+d)
Kp = Kc (RT) (c + d) (a+b)
Kp = Kc (RT)n
COCl2 (g)
Answer
;
0.14
[COCl2]
=
Kc =
0.012 x 0.054
[CO][Cl2]
= 220 M -1
Kp = Kc(RT)n
n = 1 2 = -1
[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]
H2O a pure liquid, has a constant concentration
and thus is not included in the expression.
Therefore, the equilibrium constant is written as,
[CH3COO-][H3O+]
Kc =
[CH3COOH]
Unit : M
2.
Carboxylic
Ester
acid
Kc =
[CH3COOC2H5]
[CH3COOH] [C2H5OH]
3.
CaCO3 (s)
[CaO][CO2]
Kc =
[CaCO3]
[CaCO3] = constant
[CaO] = constant
Kc = [CO2]
Kp = PCO2
CaCO3 (s)
PCO2 = Kp
PCO2 does not depend on the amount of CaCO3 or CaO
5.
Answer
;
Kp = PNH PH S = 0.265 atm x 0.265 atm
2
3
= 0.0702 atm2
Kp = Kc(RT)n
n = 2 0 = 2
T = 295 K
Kc =
0.0702 atm2
(0.08206 atm L mol1 K1 x 295 K )2
1.2 x 104 M2
Answer;
Kc = [NO]2 [Br2]
Kc =
[NOBr]2
1 =
Kc
1
[NO]2 [Br2]
[NOBr]
[Br2]1/2 [NO]
[NOBr]2
[NO]2 [Br2]
[NOBr]2
1
Kc
[NOBr]
= Kc
[NO] [Br2]
Kc =
1
Kc
Kc =
1
1.0 x 103 M
= 31.6 M-
= 31.6 dm3/2 mol
Answer;
[H2]0 = 0.200 /10.0 = 0.0200 M
[I2]0 = 0.200 /10.0 = 0.0200 M
H2 (g)
[ ]0 / M
[ ] / M
[ ] / M
0.0200
-x
0.0200 - x
+ I2 (g)
2HI (g)
0.0200
-x
0.0200 - x
+2x
+2x
Kc =
[HI]2
[H2] [I2]
49.5 =
7.036 =
(2x)2
(0.0200 x) (0.0200 x)
2x
0.0200 - x
x = 0.0156
H2 (g)
I2 (g)
2HI (g)
[ ]0 / M
0.0200
[ ] / M
-x
[ ] / M
0.0200 - x
0.0200 - x
+2x
= 0.0044
= 0.0044
= 0.0312
0.0200
-x
0
+2x
Answer;
Initial pressures of H2 and I2.
PH = nH RT = (1.000)(0.08206)(721)
2
2
V
1.000
= 59.19 atm
PI = nI2 RT
2
= (2.000)(0.08206)(721)
1.000
= 118.4 atm
H2 (g)
P0
P
P
Kp
= PHI
PH2 P I2
59.19
-x
59.19 - x
50.5 =
+ I2 (g)
2HI (g)
118.4
-x
118.4 - x
+2x
+2x
(2x)2
(59.19 x) (118.4 x)
6.2.6
Degree of Dissociation,
C = changes in concentration
C0 = initial concentration
AB
C0 / M
C / M
C / M
A+
-x
+x
+x
a-x
+x
+x
x
=
a
H+
0
C0 / M
HCOOH
0.5
C / M
-0.0089
+0.0089
C / M
0.5-0.0089
0.0089
HCOO
0
+0.0089
0.0089
= 0.4911
x
a
0.0089
=
= 0.0178 = 1.78%
0.5
cC (g) + dD (g)
[C]c[D]d
[A]a[B]b
If Q = K
If Q < K
If Q > K
Reaction is reversed
- more products are present in the
mixture at t
reaction
Br2 (g)
2Br (g)
Br2 (g)
C0/M
[Br]2
Qc =
[Br2]
Qc > Kc
0.063
=
2Br (g)
0.012
Br2 (g)
C0/M
0.063
C/M
+x
C/M
0.063 + x
2Br (g)
0.012
- 2x
0.012 - 2x
[Br]2
Kc =
[Br2]
1.1x10-3
(0.012 2x)2
=
0.063 + x
x = 1.78x10-3
[Br] = 0.012 2x
[Br2] = 0.063 + x
If x = 0.0105
= -0.009 M
= 0.0735 M
If x = 1.78x10-3
= 0.00844 M
= 0.0648 M
11.
Qc =
=
[HI]2
[H2] [I2]
(1.47 + 0.5)2
(0.200) (0.200)
= 97.0
H2 (g)
+ I2 (g)
2HI (g)
C0/M
0.200
0.200
1.47 + 0.500
C/M
C/M
+x
0.200 + x
+x
0.200 + x
-2x
1.97 2x
= 0.2535
= 0.2535
= 1.863
Kc =
54.0 =
Kc = 54
Qc = 97
[HI]2
[H2] [I2]
(1.97 2x)2
(0.200 + x) (0.200 + x)
7.35 =
1.97 2x
0.200 + x
x = 0.0535M
6.3.1
Le Chteliers Principle
A) Effect of Concentration:
Changing the concentration of the reactants or
products causes the equilibrium to shift to the
direction that will reduce the effect .
Example:
Increasing the concentration of reactant/s causes
the equilibrium position to shift forward in order to
reduce the disturbance (to eliminate the additional
concentration of reactant/s)
more products will be formed until the equilibrium is
reached again (i.e: composition of equilibrium
reaches Kc value which remains the same at a
fixed temperature).
Example ;
N2 (g) + 3H2 (g)
2NH3 (g)
Change
Equilibrium Shift
To the left
To the right
To the right
To the left
Example :
Consider the reaction below:
Fe 3+(aq)
(Yellowish)
+ SCN-(aq)
Fe(SCN)2+(aq)
(Blood red)
Answer;
Consider the reaction below:
Fe 3+(aq)
+ SCN-(aq)
(Yellowish)
Fe(SCN)2+(aq)
(Blood red)
Fe(SCN)2+(aq)
(Blood red)
B) Effect of Temperature:
The effect of temperature on an equilibrium
depends on the type of reactions, whether it
is:
i) an endothermic reaction
or
ii) an exothermic reaction
Temperature is the only factor that affects the
value of Kc
i) Endothermic reaction
An endothermic reaction is a reaction that
absorbs heat to form products.
Example:
Consider the following system:
N2O4(g)
2NO2(g)
H = +57 kJ
N2O4(g)
2NO2(g)
H = +57 kJ
N2O4(g)
2NO2(g)
H = +57 kJ
Concentration of
N2O4 increases,
thus Kc value
decreases
Example:
Consider the reaction:
Co(H2O)62+(aq)+ 4HCl(aq)
pink
To overcome the
low temperature
reaction should
release heat
Disturbance:
Low temperature
System at
equilibrium
High
temperature
C) Effect of Pressure
The pressure of a system may be changed by:
i) changing the moles of reactant or product
ii) changing the volume
iii) adding inert gas to the system
Affects only the reversible reaction involving
gaseous reactants/products
2SO3(g)
Example
N2(g) + 3H2(g)
2NH3(g)
Example
Consider the reaction:
2SO2(g) + O2(g)
2SO3(g)
Example:
For the following chemical equation,
N2 (g) + O2 (g) 2NO (g)
[NO]2
[N2] [O2]
Kc
[NO]
Equilibrium position
shifts from LEFT to the RIGHT
D)
Le Chteliers Principle
Change
Equilibrium shift
Change Equilibrium
Constant, K
Concentration
yes
no
Pressure
yes
no
Volume
yes
no
Temperature
yes
yes
Catalyst
no
no
Example :
Consider the chemical reaction at equilibrium given below
CaCO3 (s) CaO (s) + CO2 (g)
H =+ve
(a)
(b)
Kp = PCO
= 0.220 atm
Kp = Kc(RT)n
n = 1 0 = 1
Kp= Kc(RT)
Kc =
Kp
(RT)
0.220 atm
0.08206 atm L mol 1 K 1 x 798 K
= 3.36 x 103 M
(b)(i)
(ii)
(iii)
(iv)
(v)
HABER PROCESS
A process that produces ammonia from
H2 and N2
The process is introduced by German
scientists Fritz Haber and Karl Bosch.
(sometimes called Haber-Bosch) in 1912.
Main objectives of the industry are to obtain a
high yield of the product while keeping the cost
down
Consider
N2(g) + 3H(g)
2NH3(g)
H = -92.6 kJ
7.0
IONIC EQUILIBRIA
7.1
H+ (aq) + Cl (aq)
Base:
any substance that produces hydroxide ions (OH-)
when dissociating in water.
Example:
NaOH (aq)
2. Bronsted-Lowry Theory
Acid:
any substance that can donate a proton, (H+) to
other substance
Example:
HNO3 (aq) + H2O (l) NO3 (aq) + H3O+ (aq)
acid
acid
Base:
any substance that can accept a proton from
other substance
Example:
NH3 (aq) + H2O (l)
base
base
Conjugate base
A species that remains when one proton has
been removed from the Bronsted acid.
Conjugate acid
A species that remains when one proton has
been added to the Bronsted base.
Example
HCO3 (aq) + H2O (l)
acid
base
conjugate
acid
Exercise
1. In the following reactions, identify the acid-base conjugate
pairs.
a. ClO (aq) + H2O (l)
base
HOCl (aq) +
acid
acid
OH (aq)
conjugate
acid
conjugate
base
conjugate
base
NH4+(aq) + Br (aq)
c. HBr(aq) + NH3(aq)
acid
conjugate
acid
base
d. PO43(aq) + H2O(l)
base
HPO42(aq) + OH(aq)
conjugate
acid
acid
e. CH3COOH(aq) + H2O(l)
acid
conjugate
base
base
conjugate
base
CH3COO(aq) + H3O+(aq)
conjugate
base
conjugate
acid
10
conjugate base
a)
HS
S2-
H+
a)
HCN
CN-
H+
a)
N2H5+
N2H4
H+
a)
H3PO4
H2PO4-
H+
a)
H3O+
H2O
H+
a)
CH3NH3+
CH3NH2
H+
11
12
3. Lewis Theory
Acid:
a substance that can accept a pair of electrons to
form a covalent bond.
The species that can be Lewis acid are
Cations such as H+, Fe2+, Al3+
molecules with incomplete octet central atom
such as BF3, BeCl2
Molecules with central atom that can expand
octet such as PCl3
13
Base:
a substance that can donate a pair of electrons to
form a covalent bond.
The species that can be Lewis base are
anions such as OH-, CN-, Cl molecules with lone pairs electrons at
the central atom such as H2O, NH3, ROH
molecules with nonpolar multiple bond such as
alkenes
14
Example
1) H3N:
Lewis
base
2) H+
Lewis
acid
BF3
H3N BF3
H2O
Lewis
acid
OHLewis
base
SnCl62-(aq)
Lewis
acid
15
Exercise
Classify each of the following species as Lewis acid
or Lewis base.
Lewis base
i. NH3
ii.
AlCl3
iii.
BCl3
Lewis acid
Lewis acid
iv.
Ag+
v.
I-
Lewis acid
Lewis base
16
% dissociation =
[ ]dissociated
100%
[ ]initial
Degree of dissociation, =
[ ]dissociate d
[ ]initial
17
Strong Acid
H+ (aq) + Cl (aq)
2 O (l)
H
H+ (aq) + Cl (aq)
18
- 0.10
+ 0.10
+ 0.10
[ ]f 0.00
0.10
0.10
19
[HCl]dissociated
% dissociation =
[HCl]initial
100%
0.10=
100%
0.10
= 100 %
[HCl]dissociated
Degree of dissociation, =
[HCl]initial
0.10 =
0.10
= 1.00
20
21
Strong Base
H2O
[ ]i
0.50
- 0.50
+ 0.50
+ 0.50
[ ]f
0.00
0.50
0.50
22
[ NaOH ]dissociated
% dissociation =
[ NaOH ]initial
100%
0.50=
100%
0.50
= 100 %
Degree of dissociation, =
[ NaOH ]dissociated
[ NaOH ]initial
0 .50=
0 .50
= 1.00
23
24
Weak Acid
<1
A (aq) + H3O+(aq)
25
Ka =
[A ][H3O ]
[HA]
26
27
Weak Base
<1
28
Kb =
[BH ][OH ]
[B]
29
30
Example:
At 25 C, 4.2% of 0.10 M formic acid, HCOOH
dissociated in aqueous solution.
Calculate the acid dissociation constant, Ka for
formic acid.
31
Solution:
[4.2]
[HCOOH] dissociated
0.10M
[100]
0.0042 M
HCOOH + H2O
H3O+ + HCOO-
[ ]i
0.10
-0.0042
+0.0042
+0.0042
[ ]
0.0958
0.0042
0.0042
32
[HCOO - ][H 3O ]
Ka
[HCOOH]
[0.0042M]2
[0.0958M ]
1.8 10 -4 M
Ka for HCOOH is 1.8 x 10-4 M
[H 3O ] [HCOO ]
[HCOOH]
34
Try this
1.
2.
36
2H2O (l)
37
Kw
= H3O+ OH
= (1 x 10-7) (1 x 10-7)
=
1 x 10-14 M2
Note:
Temperature , Kw because the dissociation
of water is an endothermic process
38
The pH Scale
a.
pH = log H3O+
39
40
In pure water,
Kw = H3O+ OH = 1 x 10-14
M2
H3O+ = OH = 1 x 10-7
M
pH
= pOH = log (1 x
10-7 )
pH
= pOH = 7
pH + pOH = 14
41
At 25 oC,
Acidic solution : pH < 7.0 ; pOH > 7.0
Basic solution : pH > 7.0 ; pOH < 7.0
Neutral solution : pH = 7.0 ; pOH = 7.0
42
Example 1
In a NaOH solution, [OH-] is 2.9 x 10-4 M.
Calculate the pH of the solution at 25 oC.
(10.46)
43
Example 2
The pH of rainwater in a certain region was 5.68.
Calculate the H+ ion concentration of the rainwater.
(2.089 x 10-6)
44
Example 3
Calculate the pH of a 0.15 M acetic acid (CH3COOH)
solution, Ka = 1.8 x 10-5.
(2.79)
45
Example 4
What is the pH of a 0.25 M ammonia solution?
Kb = 1.8 x 10-5.
(11.33)
46
Example 5
The pH of 0.06 M solution of formic acid (HCOOH)
is 3.44. Calculate the Ka of the acid.
(2.211 x 10-6)
47
Exercises
1.
1.
48
1.
a.
b.
c.
d.
e.
Answer
0.55 M CH3COOH (Ka = 1.8x10-5)
2.5
0.23 M NH3 (Kb = 1.8x10-5)
11.31
0.15 M HCl
0.82
0.20 M KOH
13.3
0.45 M HCN (Ka = 4.9 x 10-10)
4.8
49
SALTS
50
1) Neutral salts
51
Kw = H3O+ OH = 1 x 10-14 M2
[H+ ] = [ OH- ] = 1.0 x 10-7 M
pH = 7
52
SALT HYDROLYSIS
53
2) BASIC SALTS
eg :
CH3COONa(aq)
Na+
CH3COO-
54
Hydrolysis of CH3COO- :
CH3COO-(aq) + H2O (l)
CH3COOH(aq) + OH-(aq)
55
Example
Sodium cyanide, NaCN is a salt formed when a
strong base, NaOH is reacted with a weak acid, HCN.
a)
56
3) ACIDIC SALTS
Eg.
NH4Cl(s)
Cl-
NH4+(aq) + Cl(aq)
57
Hydrolysis of NH4+ :
NH4+(aq) + H2O(l)
NH3(aq) + H3O+(aq)
58
Example
CH3NH3Cl is a salt formed when a weak
base,CH3NH2 is reacted with a strong acid, HCl.
a)
b)
59
BUFFER SOLUTION
A solution that maintains its pH when a small amount
of a strong acid or a strong base is added to it.
It contains weak acid or weak base with salt that has
its conjugate pair.
2 types of buffer solution:
a. acidic buffer solution
b. basic buffer solution
60
Has pH < 7.
Example:
A solution of CH3COOH and CH3COONa
61
H+(aq) + CH3COO-(aq)
CH3COONa(aq)
CH3COO-(aq) + Na+(aq)
62
63
BUFFERS ACTION
CH3COOH(aq) + H2O(l)
CH3COO-(aq) + H2O(l)
65
Comes from
weak acids
H+
A-
66
[ H ][ A ]
[ HA ]
or
[H+]
Ka[HA]
=
[A ]
[H+]
pH
[ HA]
= -log Ka + ( - log
[ A ]
[
A
]
= pKa + log
[HA]
Henderson-Hasselbalch equation
67
Example
a.
b.
c.
68
Has pH > 7
NH4+(aq) + OH-(aq)
NH4+(aq) + Cl-(aq)
69
70
BUFFERS ACTION
71
(i)
NH3(aq) + H3O+(aq)
NH4+(aq) + H2O
72
73
BH+ + OH-
74
[OH-] = Kb
or
[ B]
[ BH ]
pOH
[ B]
)
[ BH ]
[
BH
]
= pKb + log
[B ]
Henderson-Hasselbalch equation
75
Example
A buffer solution is prepared by mixing 400mL 1.5 M
NH4Cl solution with 600 mL of 0.10 M NH3 solution.
[ Kb = 1.8 x 10-5 ]
a) Calculate the pH of buffer
b) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.10 M HCl
c) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.15 M NaOH
76
Exercises
a) Calculate the pH of a 1 L buffer solution
containing 1.5 M CH3COOH and 0.20 M of
CH3COONa.
pH = 3.87
b) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.1 M HCl.
PH = 3.87
a) Calculate the new pH of the buffer after the
addition of 2.0 mL of 0.2 M NaOH. pH = 3.87
[ Ka = 1.8 x 10-5 ]
77
a)
Calculate the pH of the solution prepared by mixing
500 mL 0.1 M hydrazinium chloride, N2H5Cl with
500 mL 0.2 M hydrazine, N2H4.
pH = 8.53
78
79
Titration apparatus
Titrant
Analyte
80
Indicators
is a weak organic acids or bases that change
colour over a range of pH values.
81
In Acid
In Base
pH Range *
Red
Yellow
1.2-2.8
Yellow
Bluish
Purple
3.0-4.6
Orange
Yellow
3.1-4.4
Red
Yellow
4.2-6.3
Chlorophenol blue
Yellow
Red
4.8-6.4
Bromothymol blue
Yellow
Blue
6.0-7.6
Cresol Red
Yellow
Red
7.2-8.8
Colourless
Reddish
pink
8.3-10.0
Thymol blue
Bromophenol blue
Methyl orange
Methyl red
Phenolphthalein
82
TYPES OF TITRATIONS
1.
2.
3.
83
* The pH starts
out
84
85
86
87
88
* The pH at the
equivalence point > 7.0.
The solution contains the
basic salt.
89
90
91
92
pH jump
3-11
3-7
7-11
Example 1 :
Sketch the titration curve of 25 mL 0.1 M HCl with
0.1 M NaOH.
Step 1 :
Analyte is a strong acid,
HCl dissociates completely
HCl(aq) + H2O(l) Cl (aq) + H3O+(aq)
[H3O+] = [HCl] = 0.1 M
pH = - log [H3O+] = 1.0
94
= n NaOH
= MNaOH VnaOH
VNaOH = 0.1 x 25
0.1
= 25 mL
95
Step 3 :
Type of titration : strong acid-strong base
pH jump : 3 11
Step 4 :
Titrant is a strong base, NaOH.
NaOH (aq)
97
Step 2:
at equivalence point
HCl(aq) + NH3 (aq)
NH4Cl (aq)
- pH equivalence
- the solution is NH4Cl (aq)
- only NH4+ hydrolyses to form H3O+
- therefore pH < 7.0
- Volume equivalence
n NH = n HCl
MNH VNH = MHClVHCl
VNH = 0.2 x 25 = 50 mL
0.1
3
Step 3 :
Type of titration : strong acid-weak base
pH jump : 3 7
Step 4 :
Titrant is a weak base, NH3.
Final point approaching pH < 11
99
pH jump
Suitable Indicators
Strong
Acid-Strong
Base
Weak
Acid-Strong
Base
Strong Acid-weak Base
3 10
7 11
3 7
Exercise 1
What is the colour of the solution when 3 drops of the
below indicators are added separately to water (pH = 7)
?
Indicator
pH range
Phenolphthalein
8.2 10.0
Colour change
Colourless
reddish
pink
Methyl orange
3.2 4.2
Red
Yellow
Bromothymol blue
6.0 7.6
Yellow
Blue
phenol red
6.8 8.4
Yellow
Red
Exercise 2
The pH range and the colour change for 3 indicator
X, Y and Z is shown in the table below. Determine X,
Y and Z.
Indicator
pH range
colour change
1.2 2.8
Red
6.0 7.6
Yellow
8.3 10.5
Colourless
Yellow
Blue
Yellow
SOLUBILITY EQUILIBRIUM
103
104
105
M+ (aq) + X- (aq)
Kc = [M+] [X-]
[MX]
Kc [MX] = [M+] [X-]
*since [MX] is a constant ;
Ksp = [M+] [X-]
106
107
Example
Write the solubility product expression and state
the units of Ksp for each of the following ionic
compounds.
a) Ca3(PO4)2
b) Ag2CO3
108
Example
The solubility product of silver chromate(VI),
Ag2CrO4 is 2.4 x10-12 mol3dm-9. Calculate the
concentration of Ag+(aq) and CrO42-(aq) in the
saturated solution.
Ans: [Ag+] = 1.68 x 10-5 M
[CrO42-] = 8.43 x 10-5 M
109
Example
The solubility of silver sulphide, Ag2S is 5.0x10-17.
Calculate the solubility product of Ag2S.
Ans: 5.0 x 10-49
110
Example
Calculate the solubility of copper (II) hydroxide,
Cu(OH)2, in g L-1.
Ksp Cu(OH)2 = 2 x 10-20 M3,
Mr Cu(OH)2 = 97.57g mol-1
111
112
soluble salt, MA :
MA (s)
M+ (aq)
A- (aq)
113
Example
Will precipitate form when 50 mL 0.001 M NaOH
is added to 150 mL of 0.01 M MgCl2.
(Ksp Mg(OH)2 = 2 x 10-11)
115
Example
Exactly 200 mL of 0.0040 M AgNO3 are added to
800 mL of 0.008 M K2SO4. Will a precipitate form?
(Ksp Ag2SO4 = 1.4x10-5 M3)
116
117
Example
118
AgCl (s)
Ag+ (aq)
+ NO3- (aq)
(common ion)
- [Ag+] will increase.
- Equilibrium position will shift backward
(according to the Le Chatelier's Principle).
- Solubility of AgCl will decrease.
- So, the addition of a common ion will
reduce the solubility of a slightly soluble salt.
119
Example
Calculate the solubility of AgCl (mol L-1) in :
a.
liquid water
b.
120
9.0 THERMOCHEMISTRY
Concept of Enthalpy
Important Terms
Thermochemistry
Exothermic
Endothermic
Exothermic reactions
H = ve
reactants
enthalpy
H = -ve
products
reaction pathway
Endothermic Reactions
Enthalpy, H
Enthalpy of reaction:
The enthalpy change associated with a chemical
reaction.
Standard enthalpy, H
The enthalpy change for a particular reaction that
occurs at 298K and 1 atm (standard state)
Thermochemical Equation
H = +6.01 kJ
Types of Enthalpies
Enthalpy of Formation, Hf
Hf = 286 kJ mol1
Enthalpy of Combustion, Hc
Hc = 393 kJ mol1
Enthalpy of Atomisation, Ha
Na(s) Na(g)
Ha = +109 kJ mol-1
Cl2(g) Cl(g)
Ha = +123 kJ mol-1
Enthalpy of Neutralization, Hn
The heat change when 1 mole of water, H2O is formed from the
neutralization of acid and base .
I2 (s)
I2(g)
Hsubl =
+106 kJ mol1
Calorimetry
Simple calorimeter
Bomb calorimeter
Simple calorimeter
A bomb calorimeter
Heat released by
substance
Heat absorbed
by calorimeter
q = mcT
q = heat released by substance
m= mass of substance
C= specific heat capacity
T = temperature change
Heat absorbed
by surroundings
Example 1
In an experiment, 0.100 g of H2 and excess of O2 were compressed
into a 1.00 L bomb and placed into a calorimeter with heat capacity
of 9.08 x 104 J0C1. The initial temperature of the calorimeter was
25.0000C and finally it increased to 25.155 0C. Calculate the
amount of heat released in the reaction to form H2O, expressed in kJ
per mole.
Solution
Heat released = Heat absorbed by the
calorimeter
q
= CT
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ
H2(g) + O2(g) H2O(c)
mole of H2 = 0.100
2.016
= 0.0496 mol
moles of H2O
mole of H2
14.1
= 0.0496
Heat of reaction, H
= 284 kJ
= - 284 kJ mol1
kJ
Example 2
1. Calculate the amount of heat released in a reaction in
an aluminum calorimeter with a mass of 3087.0 g and
contains 1700.0 mL of water. The initial temperature of
the calorimeter is 25.0C and it increased to 27.8C.
Given:
Specific heat capacity of aluminum = 0.553Jg-1 C-1
Specific heat capacity of water
= 4.18 Jg-1 C-1
Water density = 1.0 g mL-1
T = (27.8 -25.0 )C = 2.8C
Solution
Heat released
Heat absorbed by
aluminium
calorimeter
q = mwcwT + mcccT
= (1700.0 g)(4.18 Jg-1 C-1)(2.8 C) +
(3087.0 g)(0.553 Jg-1 C-1)(2.8C)
= 24676.71 J
= 24.7 kJ
Heat absorbed by
water
HESSS LAW
Hess Law
A
H 2
H 3
H1 H2 H3
Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C
O
CO
(S)
2( g )
2( g )
1 O
H O
2
2( g )
2( g )
2 ( g)
iii.C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H
H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol
-1
Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C
O
CO
(S)
2( g )
2( g )
1 O
H O
2
2( g )
2( g )
2 ( g)
iii.C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H
H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol
-1
H ?
f
C 3H
C H
(s)
2( g )
2 6( g )
iii. Add the given reactions so that the result is the desired
reaction.
(i ) 2
2C ( S ) 2O2( g ) 2CO2( g )
H1 2 -393 kJ
( ii ) 3
3 H 2( g ) 3 O2( g ) 3 H 2O( g )
2
H 2 3 -286kJ
HOf
2C(s)
3H2 (g)
C2H6 (g)
HO2 = 3(-286)
HO1
= 2(-393)
2O2(g)
3/2 O2(g)
7/2 O2(g)
HO3 = - (-1560)
H f = 2( H1 ) + 3(H 2 ) + H3
-786 - 858 1560
1
-84 kJmol
Example 1
The thermochemical equation of combustion of carbon
monoxide is shown as below.
C(s) + O2(g) CO(g)
= ?
H
given :
H
C(s) + O2(g) CO2(g)
H= -394 kJ mol-1
Example 2
Calculate the standard enthalpy of formation of methane if the
enthalpy of combustion of carbon, hydrogen and methane are
as follows:
-1
H
[C
]
=
-393
kJ
mol
(s)
Hc
H [H2(s)]
= -293 kJ mol-1
Hc
-1
H
[CH
]
=
-753
kJ
mol
4(s)
Hc
Example 3
Standard enthalpy of formation of ammonia, hydrogen
chloride and ammonium chloride is -46.1 kJ mol-1, -92.3 kJ
mol-1, 314.4 kJ mol-1 respectively. Write the thermochemical
equation for the formation of each substance and calculate
the enthalpy change for the following reaction.
NH3(g) + HCl (g) NH4Cl(s)
Exercise
1.Calculate the enthalpy of formation of benzene
if :
H (CO2(g) ) = -393.3 kJ mol-1
H (H2O(l) ) = -285.5 kJ mol-1
-1
H
(C
H
)
=
-3265.3
kJ
mol
6
6(l)
H
f
H f
H f
Born-Haber
Cycle
e.g:
NaCl(s) Na+(g) + Cl-(g)
Na+ and Cl- ions in the solid crystal are separated from
each other and converted to the gaseous state (Hlattice)
ne
La
He
a
y
rg
E
e
ttic
to
fH
yd
ra
tio
Heat of Solution
Na+ and Cl- ion in
the solid state
Born-Haber Cycle
Example :
Na
i.
ii.
iii.
iv.
v.
vi.
(s)
Cl
2(g)
NaCl
Given;
Enthalpy of formation NaCl
Enthalpy of sublimation of Na
First ionization energy of Na
Enthalpy of atomization of Cl
Electron affinity of Cl
Lattice energy of NaCl
=
=
=
=
=
=
(s)
-411 kJmol-1
+108 kJmol-1
+500 kJmol-1
+122 kJmol-1
-364 kJmol-1
?
+ Cl(g)
Ionisation
Energy of Na
Na(g)
Electron Affinity of Cl
Na+(g) + Cl- (g)
+ Cl(g)
HaCl
+ve
Na(g) + Cl2(g)
Lattice energy
HaNa
E=0
-ve
Na(s) + Cl2(g)
Hf NaCl
NaCl(s)
NaCl
Calculation:
H 0f H S IE H a ( Cl ) EA H lattice
H lattice H 0f H S IE H a ( Cl ) EA
H lattice 411 kJ 108 kJ 500 kJ 122 kJ 364 kJ
H lattice 777 kJ
Exercise:
i.
ii.
iii.
iv.
v.
vi.
Electrochemistry
Electrochemistry
Is the study of the relationship between electricity
and chemical reaction
Chemical reactions involved in electrochemistry are :
Reduction
REDOX REACTION
Oxidation
One type of reaction cannot occur without
the other.
REDOX Reaction
REDUCTION
OXIDATION
gain of electron
loss of electron
Reaction at cathode
Reaction at anode
Remember
RED CAT
Example:
Mg Mg2+ + 2e-
= REDuction
at CAThode
RED
CAT
Oxidation no.
Example:
Cu2+ + 2e- Cu
Oxidation no.
Example
Reduction : Cu2+(aq) + 2e- Cu(s)
Oxidation :
Overall cell
2+
2+
Cu
+
Zn
Cu
+
Zn
(aq)
(s)
(s)
(aq)
reaction :
Half-cell
reaction
Cells
There are 2 type of cells
Electrochemical
Cells
where chemical reaction
produces electricity
Electrolytic
Cells
Uses electricity to
produce chemical
reaction
Also called;
Galvanic cell or Voltaic cell
Chemical
Energy
Electrical
Energy
Electrical
Energy
Chemical
Energy
Galvanic cell
Voltmeter
Cu
electrode
Zn
electrode
Zn2+
ZnSO4(aq)
solution
Cu2+
Salt
bridge
CuSO4(aq)
solution
Zinc dissolves.
Oxidation occurs at the Zn electrode.
Zn2+ ions enter ZnSO4 solution.
Zn is the ve electrode since it is a source of
electrons anode.
Reactions Involved:
Anode :
Cathode :
Overall cell
reaction :
Salt bridge
An inverted U tube containing a gel
permeated with solution of an inert
electrolyte such as KCl, Na2SO4, NH4NO3.
Functions
Salt bridge helps to maintain electrical neutrality
Completes the circuit by allowing ions carrying charge
to move from one half-cell to the other.
Zn
ZnSO4(aq)
Zn2+
e
e
e
e
e
e
Cu2+
CuSO4(aq)
ANODE (-)
E = +1.10 V
Zn
ZnSO4(aq)
Zn2+
Cu
e
e
Cu2+
Salt bridge
(KCl)
CuSO4(aq)
Right Cell
Cu2+ (aq) + 2e- Cu (s)
Cu 2+ ions leave the solution.
Causing an overall excess of
-ve charge.
K+ ions from salt
bridge move into Cu
half cell
Electrochemical Cells
anode
oxidation
cathode
reduction
spontaneous
redox reaction
half
19.2
Cell notation
Zn (s) + Cu2+ (aq)
Phase boundary
cathode
Cell notation
Exercise
For the cell below, write the reaction at anode
and cathode and also the overall cell reaction.
Cell notation
X3
X2
measured by a voltmeter
Cu2+(aq) + 2e Cu(s)
Eored = +0.34 V
Zn2+(aq) + 2e Zn(s)
Eored = -0.76 V
Standard reduction
potential
Cu2+(aq) + 2e Cu(s)
Eored = +0.34 V
Zn2+(aq) + 2e Zn(s)
Eored = -0.76 V
E0 = -0.76V
E0 = +0.34V
or
= +0.34 (-0.76)
= +1.10 V
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:
Anode :
Cathode :
For example:
Cl2(g) + 2e- 2Cl-(aq)
E0 = +1.36 V
Cl2(g) + e- Cl-(aq)
E0 = +1.36 V
Cl-(aq) Cl2(g) + e-
E0 = -1.36 V
H2 gas
at 1 atm
H+ (aq)
1 M
Pt
electrode
e
e
e
2+
Zn e
ZnSO4(aq)
1M
E0 = 0
+
+
H2 (g), 25oC,1
H+(aq),1 M
Pt
atm.
Zn2+ (1 M) + 2e-
Zn (s)
2e- + 2H+ (aq,1 M)
H2 (g,1 atm)
Zn2+(aq) + H2 (g,1 atm)
0 = E 0+ - E 0 2+
Ecell
H /H2
Zn /Zn
0 2+
0.76 V = 0 - EZn
/Zn
0 2+
EZn
/Zn = -0.76 V
Zn2+ + 2e- Zn
E0 = -0.76 V
+
+
Cu
E0 = 0
V-
H2 (g) 25oC
1 atm.
H+(aq)
1M
Cu2
CuSO4(aq)
1M
Pt
H2 (1 atm)
0
0 = E0
Ecell
cathode - Eanode
0 = E 0 2+
0
Ecell
Cu /Cu EH +/H2
0 2+
0.34 = ECu
/Cu - 0
0 2+
ECu
/Cu = 0.34 V
E0 = -0.76V
E0 = +0.34V
or
= +0.34 (-0.76)
= +1.10 V
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:
Anode :
Cathode :
At standard-state condition
Exercise
Calculate the standard cell potential of the following
electrochemical cell.
Co(s) | Co2+(aq) || Ag+(aq) | Ag(s)
Ag+(aq) + e- Ag(aq)
Answer
+
Cathode (Red) : Ag (aq) + e Ag(aq)
E0 = +0.80V
E0 = -0.28V
E0 = +0.80V
E0ox = +0.28V
Increase
strength as
reducing
agent
Exercise
Arrange the 3 elements in order of increasing
strength of reducing agents
X3+ + 3e- X
E0 = -1.66 V
Y2+ + 2e- Y
E0 = -2.87 V
L2+ + 2e- L
E0 = +0.85 V
Answer :
L < X < Y
Example
Calculate the E0 cell for the reaction ::
Mg(p) | Mg2+(ak) || Sn4+(ak),Sn2+(ak) | Pt(p)
Given :
Mg2+(ak) + 2e
Sn4+(ak)
E = -2.38 V
Mg(p)
+ 2e Sn2+(ak) E= +0.15 V
Oxidation
: Mg(p)
Mg2+(ak)
Reduction
: Sn4+(ak)
+ 2e
= +2.38 + 0.15
= +2.53 V
E o ox
=+2.53V
+ 2e
Eoox = +2.38 V
Sn2+(ak)
Eo = +0.15 V
Ecell = E o red
Ecell = +2.53 V
Exercise
A cell is set up between a chlorine electrode and a
hydrogen electrode
Pt | H2(g, 1 atm) | H+(aq, 1M) || Cl2(g, 1atm) | Cl-(aq, 1M) | Pt
E0cell = +1.36 V
(a) Draw a diagram to show the apparatus and chemicals
used.
(b) Discuss the chemical reactions occurring in the
electrochemical cell.
Answer
E0cell =1.36V
-
H2 (g),
1 atm.
+
+
Pt
Cl2 (g),
1 atm.
Pt
H+(aq), 1M
Cl-(aq), 1M
Answer
Reduction (cathode)
Cl2 (g) + 2e- 2Cl- (aq)
Oxidation(anode)
H2 (g) 2H+ (aq) + 2e-
E0 = 0
Eocell =+1.36 V
Eocell = Eocathode - E0anode
+1.36 = Eocathode 0
E0cathode = +1.36 V
So the standard reduction potential for
Cl2 is:
Eo = +1.36 V
E cell = 0
Zn + Sn4+
Sn2+ + Zn2+
EoZn/Zn2+ = - 0.76V.
The two half-cells involved are:Anod : Zn
Zn2+ + 2e
Eoox = +0.76 V
Cathode: Sn4+ + 2e
Sn2+ Eo = +0.15 V
Zn + Sn4+
Zn2+ + Sn2+
Or
Reduction
Pb2+(aq) + 2Cl-(aq)
Pb(s) + Cl (g)
Pb(s)
Pb(s)
Cl2 (g)
Pb2+(aq) + 2Cl-(aq)
+ Cl+2(g)
Oxidation
Eo = -0.13 V
Eoox = -1.36
Example :
Predict whether the following reactions occur
spontaneously :
2Ag+(aq)
2Ag(s) + Br2(aq)
0 +
EAg
Br2(aq)
= +0.8 V
0
EBr
- = +1.07 V
2 /Br
Answer :
2Ag(s)
/Ag
2Ag+(aq)
+ 2e
2Ag(s) + Br2(aq)
+ 2Br-(aq)
standard reduction
potential
2e
Eox = - 0.80 V
2Br -(aq)
E = +1.07 V
2Ag+(aq) + 2Br-(aq)
Esel = + 0.27 V
Exercise
A cell consists of silver and tin in a solution of 1 M
silver ions and tin (II) ions. Determine the spontaneity
of the reaction and calculate the cell voltage of this
reaction.
E0 = +0.80 V
Sn2+ (aq) + 2e- Sn (s) E0 = -0.14 V
(cathode)
(anode)
E0cell
= +0.80 (-0.14)
= +0.94 V
= +ve ( reaction is spontaneous)
Nernst equation
Nernst equation can be used to calculate the E
for any chosen concentration :
Ecell = Eocell
RT
nF
ln
[ product ]x
[ reactant]y
0.0257
n
2.303 log
[ product ]x
[ reactant]y
cell
log
[ product ]x
[ reactant]y
[ product ]x
[
reactant]y
Ecell = Eocell
0.0592
log Q
Example 1
Calculate the Ecell for the following cell
Zn(s) / Zn2+ (aq, 0.02M) // Cu2+(aq, 0.40 M) / Cu(s)
Answer
Zn(s)
+ Cu2+(aq)
Zn2+(aq)
+ Cu(s)
= +0.34 V + 0.76 V
= +0.34 V - (- 0.76 V)
= +1.10 V
= +1.10 V
E = Eo 0.0592
log [ Zn2+]
[ Cu2+]
= +1.10 V (-0.0385)
= +1.139 V
( 0.40)
At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0
log K
n
0
= Eocell 0.0592
n
Ecell
0.0592
n
log K
log K
Example 2
Calculate the equilibrium constant (K) for the
following reaction.
Cu(s) +
2Ag+(ak)
Cu2+(ak)
Answer
At equilibrium, E cell = 0
Eocell = Eo cathode -
Eo anode
= +0.80 ( +0.34)
= +0.46 V
2Ag(s)
log K
2
0
= 0.46 0.0592
log K
2
0.0592 log K = 0.46
2
log K = 15.54
K = 3.467
x 1015
Electrolysis
Electrolysis is a chemical process that uses electricity
for a non-spontaneous redox reaction to occur.
Such reactions take place in electrolytic cells.
Electrolytic Cell
It is made up of 2 electrodes immersed in an
electrolyte.
A direct current is passed through the electrolyte
from an external source.
Molten salt and aqueous ionic solution are commonly
used as electrolytes.
Electrolytic Cell
+
Oxidation
Reduction
Electrolyte
(M+X-)
X-,OH-
Anion
M+,H+
Cation
A
n
o
d
e
Positive electrode
The electrode which is connected to the
positive terminal of the battery
Oxidation takes place
Electrons flow from anode to cathode
C
a
t
h
o
d
e
Negative electrode
The electrode which is connected to the
negative terminal of the battery
Reduction takes place
Electrode
as circuit connectors
as sites for the precipitation of insoluble
products
example: Platinum , Graphite (inert electrode)
Electrolyte
a liquid that conducts electricity due to
the presence of +ve and ve ions
must be in molten state or in aqueous
solution so that the ions can move freely
example: KCl(l), HCl(aq), CH3COOH(aq)
e-
e+
Anode
Electrochemical Cell
Cathode
e-
Anode
e-
Cathode
Electrolytic Cell
Electrochemical Cell
Cathode = negative
Cathode = positive
Anode = positive
Anode = negative
Non-spontaneous redox
Spontaneous redox
reaction requires energy reaction releases energy
to drive it
Similarities:
Oxidation occurs at anode, reduction occurs
at cathode
Anions move towards anode, cations move
towards cathode.
Electrons flow from anode to cathode in an
external circuit.
Anion : Cl-
E0 = -0.83 V
Oxidation :
2H2O (l)
E0 = -1.23 V
Na (s)
E0 = -2.71 V
E0 = -0.83 V
Anode
Cl2 (g) + 2eO2 (g) + 4H+ (aq) + 4e-
2Cl- (aq)
2H2O (l)
E0 = +1.36 V
E0 = +1.23 V
Reactions involved
2H
O
(l)
+
2e
2
Cathode:
Cell
6H2O(l)
reaction:
2H2O(l)
4 H2O
O2(g) + 2H2(g)
E0cell = -2.06 V
Na (s)
E0 = -2.71 V
E0 = -0.83 V
Anode
Cl2 (g) + 2eO2 (g) + 4H+ (aq) + 4e-
2Cl- (aq)
2H2O (l)
E0 = +1.36 V
E0 = +1.23 V
Reactions involved
Cathode: 2H2O (l) + 2eAnode:
2Cl- (aq)
Cell
2H2O(l) + 2Clreaction:
E0 = -1.36 V
Exercise
Predict the electrolysis reaction when
Na2SO4 solution is electrolysed using platinum electrodes.
Solution
Na2SO4 aqueous solution contains Na+ ion, SO42- ion
and water molecules
On electrolysis,
the cathode attracts Na+ ion and H2O molecules
the anode attracts SO42- ion and H2O molecules
Cathode
Na+ (aq) + e-
Na (s)
E0 = -2.71 V
E0 = -0.83 V
Anode
S2O82- (aq) + 2eO2 (g) + 4H+ (aq) + 4e-
2SO42- (aq)
2H2O (l)
E0 = +2.01 V
E0 = +1.23 V
Equation
Cathode: 2H2O (l) + 2eAnode:
2H2O (l)
Cell
2H2O(l)
Reaction:
E0 = -1.23 V
E0cell = -2.06 V
mQ
Q = electric charge in coulombs (C)
m = mass of substance discharged
Q = It
Q = electric charge in coulombs (C)
I = current in amperes (A)
t = time in second (s)
1 F = 96 500 C
Example
An aqueous solution of CuSO4 is electrolysed using a
current of 0.150 A for 5 hours. Calculate the mass
of copper deposited at the cathode.
Answer
Electric charge, Q = Current (I) x time (t)
Q = (0.150 A) x ( 5 x 60 x 60 )s
Q = 2700 C
1 mole of electron 1 F 96 500 C
No. of
e-
passed through =
2700
96 500
= 0.028 mol
REACTION KINETICS
Chemical kinetics is the study of the rates of
chemical reactions, the factors that affect these
rates, and the reaction mechanisms by which
reactions occur.
Important
industrial process
-Time
-Optimum yield
-Optimum conditions
control over reaction,
obtain products economically,
using optimum conditions
Rate of reaction
1
rate
Time
Example;
d[A]
rate =
dt
d[B]
rate = dt
dt = period of time
time
d[A]
rate = dt
rate =
d[B]
dt
[B]
[A]
Rate of reaction
The average rate is the rate over a period of time.
The rate of reaction at a given time is called an
instantaneous rate of reaction.
The instantaneous rate at the beginning of a
reaction is called the initial rate of reaction.
Instantaneous rate is determined from a graph of
concentration vs time by drawing a line tangent to
the curve at that particular time.
Rate of reaction
Reaction:
H2O2(aq) H2O(l) + O2(g)
Reaction rates are obtained
from the slopes of the straight
lines;
purple
blue
red
Rate =
cC + dD
1 d[A]
1 d[B] 1 d[C] 1 d[D]
a dt
b dt
c dt
d dt
d[N 2 ]
1 d[H 2 ] 1 d[NH 3 ]
Rate =
dt
3 dt
2 dt
The equation means that the rate of disappearance
of N2 is 1/3 the rate of disappearance of H2 and 1/2
the rate of formation of NH3.
Example 1:
Consider the reaction, 2HI H2 + I2,
determine the rate of disappearance of HI when
the rate of I2 formation is 1.8 x 10-6 M s-1.
Solution:
Rate =
2 dt
dt
dt
d[I 2 ]
= 1.8 10-6
dt
1 d[HI] d[I 2 ]
Rate =
2 dt
dt
d[HI]
= 2 1.8 10-6 = 3.6 10-6 M s-1
dt
EXERCISE 1:
Hydrogen gas produced nonpolluting product is
water vapour when react in O2 due to this reaction
has been used for fuel aboard the space shuttle,
and may be used by Earth-bound engines in the
near future.
2H2(g) + O2(g)
2H2O(g)
Express the rate in terms of changes in [H2],
[O2] and [H2O] with time.
When [O2] is decreasing at 0.23 mol L-1 s-1, at
what rate is [H2O] increasing?
(0.46 mol L-1 s-1)
Exercise 2:
Consider the reaction,
NO(g) + O2(g) 2NO2(g).
Suppose that at a particular time during the
reaction nitric oxide (NO) is reacting at the rate of
0.066 M s-1
a) At what rate is NO2 being formed?
b) At what rate is molecular oxygen reacting?
Exercise 3:
Consider the reaction,
N2(g) + 3H2(g) 2NH3(g)
Suppose that at a particular moment during the
reaction molecular hydrogen is reacting at the rate
of 0.074 M s-1
a) At what rate is ammonia being formed?
b) At what rate is molecular nitrogen reacting?
11.1
RATE LAW
Objectives:
At the end of the lesson the students should be able
to:
1. define rate law and write the rate equation
2. define the order of reaction and the rate constant
3. calculate the order with respect to a certain reactant
from experimental data
4. determine the overall order of a reaction from
experimental data
5. calculate the value and determine the units of
rate constants
cC + dD
Rate [reactant]
Rate = k [A]x[B]y
reaction order is x with respect to A
reaction order is y with respect to B
Overall reaction order is (x + y)
The exponents x, y, can be integers, fractions or
decimal or negative values.
k is called rate constant
Rate Law
2FClO2 (g)
rate = k [F2][ClO2] 1
determined
Products
Rate, r = k [A]x
i) The reaction is zero order
Rate = k [A]0
Rate = k
unit k = unit rate
= mol L-1 s-1 or M s-1
rate
Rate = k [A]1
k=
[A]
Unit k =
M s-1
M
= s-1
iii) Second order
Rate = k [A]2
rate
k=
[A]2
M s-1
Unit k =
M2
= M-1 s-1
Example :
S2O82- + 3I-
2SO42- + I3-
The above reaction is first order with respect to iodide ions and
to thiosulphate ions.
a) Write the rate of equation for the reaction.
b) What is the unit of rate constant, k?
Solution :
a) Rate = k [S2O82-]1[I-]1
b) Rate = k [S2O82-]1[I-]1
rate
k=
[S2O82-]1[I-]1
Unit k =
Ms-1
M2
M-1 s-1
Products
Rate = k [A]x
i) If x = 0
Rate = k [A]0
Rate = k
Rate is not dependent on [A]
Therefore this reaction is zero order with respect to A
ii) If x= 1
Rate = k [A]1
iii) If x = 2
Rate = k[A]2
Example
Determining Reaction Order from Rate Law
For each of the following reactions, determine the
reaction order with respect to each reactant and the
overall order from the given rate law.
(a)
2NO(g) + O2(g)
CH4(g) + CO(g);
rate = k[CH3CHO]3/2
Solution:
The reaction order with respect to CH3CHO : 3/2
The reaction order (overall) : 3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq)
I3-(aq) + 2H2O(l);
rate = k[H2O2][I-]
Solution:
The reaction of order with respect to H2O2 : 1
The reaction of order with respect to I- : 1
and zero order in H+, while overall order is 2.
2NO2(g)
Initial Reactant
Concentrations (molL-1)
Experiment
O2
NO
Initial Rate
(M s-1)
1.10x10-2
1.30x10-2
3.21x10-3
2.20x10-2
1.30x10-2
6.40x10-3
1.10x10-2
2.60x10-2
12.8x10-3
3.30x10-2
1.30x10-2
9.60x10-3
1.10x10-2
3.90x10-2
28.8x10-3
Solution:
O2(g) + 2NO(g)
2NO2(g)
rate = k [O2]m[NO]n
Compare 2 experiments in which the concentration of one reactant
varies and the concentration of the other reactant(s) remains
constant.
rate2
rate1 =
k [O2]2m[NO]2n
k [O2]1m[NO]1n
6.40x10-3Ms-1
3.21x10-3Ms-1
2=
[O2]2m
[O2]1m
2.20x10-2mol/L
[O2]2
[O2]1
1.10x10-2mol/L
2m , m = 1 ;
Exercise:
ClO2(aq) + 2OH- (aq) products
The results of the kinetic studies are given below.
[ClO2]
M
0.0421
[OH-]
M
0.0185
8.21 1 0-3
0.0522
0.0185
1.26 1 0-2
0.0421
0.0285
1.26 1 0-2
exp
Initial rate,
Ms-1
Exercise:
Write rate law for this equation,
A + B C
i)
Exercise:
Many gaseous reactions occur in a car engine and exhaust
system. One of the gas reaction is given below.
NO2(g) + CO(g)
NO(g) + CO2(g)
Rate = k [NO2]m[CO]n
Use the following data to determine the individual and overall reaction orders:
Experiment
Initial Rate(Ms-1)
Initial [NO2](M)
Initial [CO](M)
0.0050
0.10
0.10
0.080
0.40
0.10
0.0050
0.10
0.20
rate
[A] M
- d[A] = k
dt
Using calculus,
- d[A] = kdt
- d [A] = k dt
- [A] = kt + c
substituting t=0, [A] = [A]0
- [A]0 = k(0)+c
c = - [A]0
[A]0 -[A] = kt
Unit of k for zero order reaction M s-1
[A]o [A] = kt
[A]o [A]
y = mx + c
t
[A]
[A]o
rate
[A] = -k t + [A]o
y=m x+c
[A]
Half-life (t)
Half life (t) is the time required for the concentration of a reactant to decrease
to half of its initial value.
zero order reaction
Substituting t = t1/2 , and [A] = [A]0 into the zero
order reaction, gives
2
[A]0 - [A] = kt
[A]0 [A]0 = kt1/2
2
Solving for t1/2 gives
t1/2 = [A]0
2k
Rate = k[A]
y = mx + c
Rate
Ms-1
[A] ,M
k[A]
dt
- d[A]
t = 0, [A]=[A]0
=
k dt
- ln [A]0 = k(0) + c
c = ln[A]0
[A]
- d[A]
substituting
= k dt
[A]
- ln [A] = kt + c
ln
[A]0
[A]
kt
ln[A] = - kt +ln[A]o
[A]
[A]0
ln -----[A]
kt
ln[A]
ln[A]o
[A]
ln[A]o
Example
The reaction 2A
B is first order with respect A with a
rate constant of 2.8 x 10-2 s-1 at 800C. How long will it take
for A to decrease from 0.88 M to 0.14 M ?
[A]0 = 0.88 M
ln[A]o ln[A] = kt
[A] = 0.14 M
kt = ln[A]0 ln[A]
ln[A]0 ln[A]
=
t=
k
ln
[A]0
[A]
k
ln
=
0.88 M
0.14 M
2.8 x
10-2
s-1
= 66 s
Example
Decomposition of H2O2 (aq) is first order, given that k = 3.66 x 10-3 s-1 and [H2O2 ]o
= 0.882 M, determine
a) the time at which [H2O2] = 0.600 M
b) the [H2O2 ] after 225 s.
Solution :
a)
ln
[H2O2]0
kt
[H2O2]
ln
0.882
0.600
= 105.26 s
b)
ln
[H2O2]0
kt
[H2O2]
0.882
ln
[H2O2]
[H2O2] = 0.387 M
Exercise,
The conversion of cyclopropane to propene in the gas phase is a first
order reaction with a rate constant of 6.7 X 10-4 s-1 at 500C.
CH2
CH2
CH2
CH3-CH=CH2
First-order reaction
A
product
No. of
half-lives
1
[A]o = 8 M
4
1/2
t = ln2
k
Example
The decomposition of ethane C2H6 to methyl radicals is a first order reaction
with a rate constant of 5.36 x 10-4 s-1 at 700o C.
C2H6 (g)
2 CH3 (g)
Calculate the half life of the reaction in minutes.
Solution
ln 2
t1/2
=
k
0.693
=
5.36 x 10-4
= 1.29 x 103 s
=
21.5 min
Problem 2
What is the half-life of a compound if 75% of a given sample of the compound
decomposes in 60 min? Assume it is first-order reactions kinetics.
(t1/2=30 min)
Problem 3
The decomposition of SO2Cl2 is a first-order reaction.
SO2Cl2(g)
SO2 (g) + Cl2 (g)
i) Write the rate differential equation for the reaction.
ii) Calculate the value of rate constant, k at 500 K if
5.00 % SO2Cl2 decomposed in 6.75 min.
Ans (7.6X10-3)
iii) Specify the half-life for the decomposition reaction. Ans (91.20 )
Example
A product
Where
d[A]
Rate = dt
= k[A]2
=
[A]2
Unit k
M/s
M2
= M-1 s-1
1
[A]0
+ kt
Rate = k [A]2
rate
[A]
rate
[A]2
[A]
[A]
+ kt
[A]o
t
1/[A] 1/[A]o
1/[A] M-1
1/[A]o
t
+ kt
=
[A]
[A]0
[A]= [A]o
Substituting t = t1/2
1
2
1
+ kt1/2
=
[A]0
[A]0
2
1
t1/2=
k[A]0
[A]0
1
t1/2=
k[A]0
[A]0/2
[A]0/4
[A]0/8
2x
4x
Example
Iodine atoms combine to form molecular iodine in
the gaseous phase
I (g) + I (g) I2(g)
This reaction is a second order reaction , with the rate constant of 7.0 x 109 M-1 s1
Solution :
1
i)
1
=
[A]
+ kt
[A]0
+ (7.0 x 109 x 2 x 60 )
=
[A]
[0.086]
= 8.4 x 1011
[I2] = 0.06 M
1
t1/2=
1
=
7.0 x 109 x 0.060
k[A]0
=
2.4 x 10-10 s
[I2] = 0.42 M
1
t1/2=
k[A]0
1
=
7.0 x 109 x 0.042
= 3.4 x 10-10 s
Using graph
Example,
The following results were obtained from an experimental investigation
on dissociation of dinitrogen pentoxide at 45oC
time, t/min
10
20
30
40
50
60
[N2O5] x 10-4 M
176
124
93
71
53
39
29
ii)
Solution :
180
160
140
120
[N2O5] x 100
10-4 /M
80
60
40
20
10
20
30
40 50 60 70
80
Time ( min)
ln2
k=
= 0.03 min-1
20 min
Order
0
Rate Law
rate = k
rate = k [A]
[A]2
rate = k
Concentration-Time
Equation
[A] = [A]0 - kt
ln[A] = ln[A]0 - kt
1
1
=
+ kt
[A]
[A]0
Half-Life
t =
[A]0
2k
t = ln2
k
1
t =
k[A]0
1st order
A product
r = k [A]1
Unit k = s-1
Zero order
A product
r = k [A]0
Unit k = M s-1
r
[A]
[A]
[A]0
[A]2
ln([A]0 / [A]) = kt
1/[A] 1/[A]0 = kt
ln[A]
[A]
[A]0 [A] = kt
[A]
2nd order
A product
r = k [A]2
Unit k = M-1 s-1
[A]
1/[A]
ln[A]0
1/[A]0
[A]0 - [A]
ln([A]0 / [A])
t1/2 =
ln2/k
t
1/[A] 1/[A]0
t1/2 = 1/k[A]0
t
Collision Theory
Importance of Orientation
Orientation is unimportant
Orientation is important
Importance of Orientation
Orientation is important
Potential energy
Ea
Reactant
product
Progress of reaction
Ea (Forward reaction)
Ea (reverse reaction)
CO(g) + NO2(g)
CO2(g) + NO(g)
Product
H
Reactant
Ea
H
2NOCl
2NO + Cl2
Example:
1. For the reaction A + B
C + D , the enthalphy
change of the forward reaction is + 21 kJ/mol. The
activation energy of the forward reaction is 84 kJ/mol.
a) What is activation energy of the reverse reaction?
b) Sketch the reaction profile of this reaction
2. Draw a potential energy diagram for an exorthermic
reaction. Indicate on the drawing:
a) Potential energy of the reactants and the products
b) The activation energy for the forward and the reverse
reaction
c) The heat of the reaction
TEMPERATURE:
Reaction rates generally increase rapidly
as the temperature is increased.
CATALYSTS:
Catalysts speed up reactions.
PARTICLE SIZE:
The rate increases as the smaller the size of
reacting particles .
A) CONCENTRATIONS OF REACTANTS
Reaction rate
collision
time
A) CONCENTRATIONS OF REACTANTS
A concentration of reactants increases, the frequency
of collision increases.
This would also result in the increase in the quantity of
effective collision. Thus the reaction rate increases.
5 particle system
(3 and 2) 6 collision
A) CONCENTRATIONS OF REACTANTS
This observation correlates with the RATE LAW that has
been previously discussed
x
Reaction rate = k [ A ] [ B ]
(A & B = reactants)
(x & y = rate order)
B) TEMPERATURE
B) TEMPERATURE
ARRHENIUS EQUATION
In 1889, Svante Arrhenius proposed the following
mathematical expression for the effect of
temperature on the rate constant, k:
k = A
-Ea
e RT
Where
k = rate constant
A = constant known as the collision frequency factor
e = natural log exponent
Ea = activation energy for the reaction
R = universal gas constant (8.314 J mol-1 K-1)
T = absolute temperature
B) TEMPERATURE
ARRHENIUS EQUATION
The relation ship between the rate constant, k and
temperature can be seen in the k vs T graph:
k = A
-Ea
e RT
1/T (K-1)
B) TEMPERATURE
Ea
ln k ln( A .e
RT
Ea
RT
Ea
RT
ln k ln A ln( e
)
Ea
ln k
ln e ln A
RT
Thus
See the linear relationship?
Ea 1
ln k
( ) ln A
R T
y = m x + C
(But ln e = 1)
B) TEMPERATURE
Where,
Ea = Activation Energy
R = 8.314 Jmol-1K-1
T = Absolute Temp
A = Collision freq. factor
B) TEMPERATURE
If the value of A (collision frequency factor) is not
known and the same reaction conducted at two
different temperatures.The Arrhenius equation at each
temperature can be written and combined to formed
the equation shown in the box.
Ea 1
ln k1
( ) ln A
R T1
and
ln k 2
Ea 1
( ) ln A
R
T2
Ea 1
ln k 1
( ) ln A
R T1
Since A is a constant
E
1
E
1
ln k 1 a ( ) ln k 2 a ( )
R T1
R T2
Ea 1
Ea 1
ln k1 ln k 2
( )
( )
R T2
R T1
Ea 1
ln k 2
( ) ln A
R T2
k1 Ea 1 1
ln
( )
k2
R T2 T1
T1 = 500K
T1 = 600K
SOLUTION:
k1 Ea 1 1
ln
( )
k2
R T2 T1
E a R ln(
k1 1
1
)(
) 1
k 2 T 2 T1
1.10 10 5
1
1 1
Ea (8.314 ) ln(
)(
)
9
9.51 10
600 500
Ea = 1.76 x 105 J/mol = 176 kJ/mol
C) CATALYST
C) CATALYST
Reaction rate = k [ A ] [ B ]
(A & B = reactants)
(x & y = rate order)
Ea 1
ln k
( ) ln A
R T
C) CATALYST
uncatalyzed
catalyzed
Ea > Ea
Reaction pathway
D) PARTICLE SIZE
The smaller the size of reacting particles, the greater is
the total surface area exposed for reaction and
consequently the faster the reaction. In the case of
heterogeneous systems, in which the reactants are in
different phases, the area of contact between the reacting
substances will influence the reaction rate considerably.
Introduction To Organic
Chemistry
Lecture 1
12.1 Introduction
Learning Outcomes:
At the end of the lesson the students should be able to :
1.
List the elements that made up organic compounds C, H,
O, N, P, S and halogens.
2.
State the ability of carbon to form 4 covalent bonds with
other carbons or elements.
3.
Differentiate between saturated and unsaturated organic
compounds.
4.
Give examples of organic compounds used in medicine,
engineering, biotechnology and agriculture.
Examples :CH4
methane (a component of natural gas)
OCOCH3
COOH
O
CH2
NH
O
N
COOH
Cl
CH
Cl
CCl3
dichlorodiphenyltrichloroetane
(DDT- a pesticide component)
Single bond
Double bond
Triple bond
Hydrocarbons
saturated
Contains only single
bonds ( -C-C- )
Examples: alkanes,
cycloalkanes
unsaturated
Contains at least one
carbon-carbon double
bond (-C=C-) or triple
bond (-C C-).
Examples: alkenes,
alkynes.
Engineering
Biotechnology
Agriculture
Lecture 2:
12.2 Molecular and Structural Formulae
Learning Outcomes:
At the end of the lesson the students should
be able to :
Define structural formula.
Draw structural formula in the form of expanded,
condensed and skeletal structures based on the
molecular formula.
Explain primary (1), secondary (2), tertiary (3)
and quaternary (4) carbon.
2- Dimensional formula
Condensed Structure
Does not show single bonds between carbon
and hydrogen atoms, but double and triple bonds
are shown.
All atoms that are attached to a carbon are
written immediately after that carbon.
C4H9Cl
CH3CHCH2CH3
(Condensed structure)
Examples:
ii) Cyclohexane, C6H12
H2C
H2
C
CH2
H2C
C
H2
CH2
Expanded Structure
Expanded structures indicate how atoms are
attached to each other but are not representations
of the actual shapes of the molecules.
C4H9Cl
Molecular
Formula
H H
Cl
Expanded structure
Examples:
i) Alcohol (C2H6O)
H
OH
OH
Skeletal Structure
Shows only the carbon skeleton.
Hydrogen atoms are not written.
Other atoms such as O, Cl, N etc. are shown.
i)
CH3CH(Cl)CH2CH3
=
Cl
ii)
H2C
CH2
H2C
CH2
3- Dimensional formula
( wedge dashed wedge line formula )
Example : Bromoethane
Br
H
C
H
Br
or
Br
or
Br
Classification of C atoms:
A carbon atom can be classified as
primary carbon(1o) bonded to 1 C
secondary carbon(2o) bonded to 2 C
tertiary carbon(3o) bonded to 3 C
quarternary carbon(4o) bonded to 4 C
H
H
CH3
10 carbon
10 carbon
CH3
H
C
CH3
30 carbon
CH3
H H CH3
CH3
1
H C C C CH2 C CH3
H H H
CH3
1
H H CH3
CH3
H C C C CH2 C CH3
2
H H H
CH3
H H CH3
3
CH3
4
H C C C CH2 C CH3
H H H
CH3
Question
Expanded
Structure
Condensed
Structure
Skeletal
Structure
CH3(CH2)CCl(CH3)2
O
H H
CH3
C C CH
H H
CH3
Lecture 3
Functional Group and Homologous Series
Learning Outcomes:
At the end of the lesson the students should be able
to :
Define functional group.
Name functional groups and classify organic
compounds according to their functional groups.
Define homologous series and explain general
characteristics of its members.
Functional group
is an atom or group of atoms in an organic
molecule which characterised the molecule
and enables it to react in specific ways
which determines its chemical properties.
ii.
iii.
Homologous Series
is series of compounds where each member
differs from the next member by a constant
CH2 unit
Members of the same homologous series
are called homologs.
Homologs Features
1.
Examples:
Alkane: CnH2n+2
Alkene: CnH2n
Alcohol : CnH2n+1OH
2.
3.
4.
5.
6.
Class of
Compound
Functional Group
Example
Structure
Alkane
Alkene
Alkyne
Name
CH3-CH3
-C=C-
carbon-carbon
double bond
CH3CH=CH2
-C C-
carbon-carbon
triple bond
CH3C CCH3
Aromatic
Haloalkane
Benzene ring
Alcohol
-OH
Hydroxyl
Phenol
-OH
Hydroxyl
-C-O-C-
Alkoxide
Ether
-CH3
CH3Cl
CH3-OH
-OH
CH3-O-CH3
Aldehyde
-C=O
H
Ketone
R-C=O
R
Carboxylic
acid
-C=O
OH
Ester
-C-O-CO
Acyl chloride
-C=O
Cl
Carbonyl
CH3-C=O
H
Carbonyl
CH3-C=O
CH3
Carboxyl
CH3-C=O
OH
Carboalkoxy
CH3-C=O
OCH3
CH3-C=O
Cl
Anhydride
O O
-C-O-C-
Amide
-C=O
N-
Amine
-NH2
Nitrile
-C N
O O
CH3C-O-CCH3
Carboxamide CH3-C=O
NH2
Amino
Cyano group
CH3-NH2
CH3C
Exercises:
1. Identify the functional group in the following
molecules
a)(CH3)3CCH2CH=CH2
b)(CH3)3CCH=CHCH2-OH
c)
O
C
OH C O C
NH2 CH C
CH2 O
CH3
CH
CH3
NH2
12.4 Isomerism
Learning Outcomes:
At the end of the lesson the students should be
able to :
Define isomerism.
Explain constitutional isomerism.
chain isomers
positional isomers
functional group isomer
Isomerism
Structural/
Constitutional Isomerism
Chain
Isomerism
Positional
Isomerism
Stereoisomerism
Functional Group
Isomerism
diastreomer enantiomer
cis-trans
isomerism
other
diastereomers
Isomerism
is the existence of different compounds with
the same molecular formula but different
structural formulae.
Different structural formula that have the same
molecular formula are called isomers.
Constitutional isomerism
Isomerism resulting from different order of
attachment of atoms.
Three types
a) Chain/skeletal isomerism
b) Positional isomerism
c) Functional group isomerism
a) Chain/skeletal isomerism
The isomers differ in the carbon skeleton
(different carbon chain).
They possess the same functional group and
belong to the same homologous series.
Example:
C5H12
CH3CH2CH2CH2CH3
CH3
CH3CHCH2CH3
CH3
CH3CCH3
CH3
2)Positional isomerism
These isomers have a substituent group/ functional
group in different positions.
Examples
C3H7Cl
CH3CH2CH2Cl
1-chloropropane
CH3CHCH3
Cl
2-chloropropane
C4H8
CH2=CHCH2CH3
CH3CH=CHCH3
1-butene
2-butene
C8H10
CH3
CH3
CH3
CH3
CH3
1,2-dimethylbenzene 1,3-dimethylbenzene
CH3
1,4-dimethylbenzene
C6H13N
NH2
CH3
CH3
H2N
CH3
CH2NH2
NH2
CnH2nO ; n 3
CnH2nO2 ; n 2
CnH2n ; n 3
Examples
CH3CH2OH
C2H6O
ethanol
C3H6O
CH3CCH3
O
propanone
C3H6O2
CH3CH2COH
O
propanoic acid
CH3OCH3
dimethyl ether
CH3CH2CH
O
propanal
CH3COCH3
O
methyl ethanoate
Exercise:
1. State how many are isomers with the following molecular
formulae, identify the type of isomerism and draw the
structural formula of the isomers.
a) C5H10
b) C5H10O2
c) CH3CH=C(Cl)CH3
d) C4H6Cl2
e) CH3CH2CH(OH)CH(Br)CH2CH3
Lecture 5
12.4 Isomerism
Learning Outcomes:
At the end of the lesson the students should
be able to :
Define stereoisomerism.
Describe cis-trans isomerism due to
restricted rotation about C=C bond and CC
bond in cyclic compounds
Identify cis-trans isomerism of a given
structural formula.
Diastereomer
Cis-Trans Isomerism
The requirements for geometric isomerism
:
i) restricted rotation about a C=C,double
bond in alkenes, or a C-C single bond
in cyclic compounds.
ii) each carbon atom of a site of restricted
rotation has two different groups
attached to it.
Examples
H
CH3
C
H3 C
cis-2-butene
CH3 H
H
CH 3 CH 3
CH3
C
trans-2-butene
H3C
CH3
cis-1,2-dimethylcyclohexane
trans-1,2-dimethylcyclohexane
H3C
CH3
C
H3C
H
No cis trans isomer
Lecture 6
12.4
Isomerism
Learning Outcomes:
Enantiomer
Optical Isomerism
Polarimeter
C*
PQRS
*designates chiral centre
R
ii) molecule is not superimposable with its mirror
image.
Enantiomers
a pair of mirror-image that are not superimposable.
Example:i) 2-butanol ,
CH3CHCH2CH3
OH
H3C
CH2CH3
CH2CH3
C*
H
OH
enantiomers
CH3
OH
CH3CHCOOH
OH
COOH
H
OH
COOH
HO
H
CH3
CH3
enantiomers
12.4.9 Racemate
A racemic mixture or racemate is an
equimolar mixture of enantiomers which is
optically inactive because the two components
rotate plane-polarized light equally (same
degree of rotation) but in opposite directions.
Hence it does not give a net rotation of planepolarized light.
e.g:
REACTIONS OF ORGANIC
COMPOUNDS
Lecture 7
12.5 Reactions of Organic Compounds
Learning Outcomes:
At the end of the lesson the students should
be able to :
Explain covalent bond cleavage:
homolytic
heterolytic
a)
Homolytic Cleavage
Occurs in a non-polar bond involving two
atoms of similar electronegativity.
A single bond breaks symmetrically into
two equal parts, leaving each atom with one
unpaired electron.
Formed free radicals.
Example:
X : X
X + X
free radicals
X X
b) Heterolytic cleavage
A:B
A:+
B+
anion
cation
A is more
electronegative.
A+ + B:cation anion
B is more
electronegative.
Reaction Intermediates
a) Carbocation
b) Carbanion
c) Free Radical
They are unstable and highly reactive.
a)
Carbocation
Also called carbonium ion.
A very reactive species with a positive
charge on a carbon atom.
Carbocation is formed in heterolytic
cleavage.
Example :
(CH3)3C Cl
(CH3)3C+ +
Clcarbocation
anion
b) Carbanion
is
an anion counterpart
a species with a negative charge on a carbon
atom.
Carbanion is formed in heterolytic cleavage.
example:
(CH3)3C Li
Li+
kation
(CH3)3C- +
carbanion
b)
Free Radical
free radicals
Cl
Cl
uv
Cl + Cl
ii)
iii)
H3C
H3C + H
Lecture 7
12.5 Reactions of Organic Compounds
Learning Outcomes:
At the end of the lesson the students should be
able to:
State the relative stabilities of primary, secondary
and tertiary free radicals, carbocations and
carbanions.
Explain the inductive effect of alkyl group
towards the stability of carbocations and
carbanions.
Define electrophile and nucleophile.
Carbocation Stability
The alkyl groups (electron-releasing group)
stabilise the positive charge on the
carbocation.
The stability of carbocation increases with the
number of alkyl groups present.
Carbocation Stability:
H
H
R
R
H C H < H C R <H C R < R C R
+
+
+
+
Methyl
Primary
Secondary
Tertiary
cation
10
20
30
Increasing stability
Carbanion Stability
o
Carbanion Stability:
H
H
R
R
< R C R
H C H < H C
<
H
R
R
C
Methyl
anion
Primary
10
Secondary
20
Increasing stability
Tertiary
30
Free-radical stability
The stability of free radical increases as
more alkyl groups are attached to the carbon
atom with unpaired electron.
H
H
R
H
C
H C
H
<
<
.
.
methyl
radical
Primary
10
C
.
R
R <R C
. R
Secondary
20
Increasing stability
Tertiary
30
Examples of electrophiles :
cations such as H+, H3O+, NO2+ etc.
carbocations.
Lewis acids such as AlCl3, FeCl3, BF3 etc.
oxidizing agents such as Cl2, Br2 and etc.
+ -C OH (hydroxy compounds)
b) Nucleophile
means nucleus loving
An electron-rich species and electron-pair
donor.
A nucleophile can be either neutral or
negatively charged.
Examples of nucleophiles :
anions
carbanions
Lecture 7
12.5 Reactions of Organic Compounds
Learning Outcomes:
At the end of the lesson the students should
be able to explain the main types of organic
reactions:
addition: electrophilic and nucleophilic
substitution: electrophilic, nucleophilic and free
radical
elimination
rearrangement
Addition
Substitution
Elimination
Rearrangement
I) Addition Reaction
A reaction in which atoms or groups add to
adjacent atoms of a multiple bond.
Two types of addition :a)
b)
Electrophilic Addition
Nucleophilic Addition
a)Electrophilic Addition
Initiated by an electrophile accepting electron
from an attacking nucleophile.
Typical reaction of unsaturated compounds such
as alkenes and alkynes.
Example :
CH3CH=CH2 + Br2
CCl4
CH3CHBrCH2Br
Room
temperature
electrophile
b)
Nucleophilic Addition
O
CH3
CN
C CH3 + HCN
CH3 C
OH
CH3
a) Free-radical Substitution
Substitution which involves free radicals as
intermediate species.
Example :
CH3CH3 + Cl2
uv light
CH3CH2Cl + HCl
b)
Electrophilic Substitution
Typical reaction of aromatic compounds.
+ Br2
electrophile
Fe
catalyst
Br + HBr
c)
Nucleophilic Substitution
Typical reaction of saturated organic compounds
bearing polar bond as functional group, such as
haloalkane with alcohol.
Example :
CH3CH2Br + OH-(aq)
nucleophile
CH3CH2OH + Br-(aq)
III)
Elimination
Reaction
An atoms or groups are removed from adjacent
IV)
Rearrangement Reaction
tautomerisme
C R
H C
OH
C R
O
Exercises
1.
3.
CH3
Chapter 12.0
HYDROCARBONS
12.1 : ALKANES
Hydrocarbon
are compounds which
contain only carbon and
hydrogen atoms.
HIDROCARBONS
AROMATIC
(contain one or more benzene ring)
ALIPHATIC
ALKANES
(saturated)
contain only
single bond
ALKENES
(unsaturated)
contain
C=C
CYCLO-ALKANES (saturated)
Alkanes which C atoms are
join in rings
CYCLO-ALKENES
(unsaturated)
ALKYNES
(unsaturated)
contain
CC
Saturated hydrocarbons
- compound with C-C
- Example : alkanes and cycloalkanes
Contain the maximum number of hydrogen
atoms that the carbon compound can
possess.
Unsaturated hydrocarbons
-compounds with multiple bonds
-Example : alkenes, cycloalkenes, alkynes
and aromatic hydrocarbons
They posses fewer than the maximum
number of hydrogen atoms.
ALKANES
Structural formula
CH4
CH3CH3
CH3CH2CH3
CH3(CH2)2CH3
CH3(CH2)3CH3
CH3(CH2)4CH3
CH3(CH2)5CH3
CH3(CH2)6CH3
CH3(CH2)7CH3
CH3(CH2)8CH3
No .of C
atoms
1
2
3
4
5
6
7
8
9
10
Name
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Example
C4H10
2-
isobutane
CH3(CH2)2CH3
CH3CH(CH3)2
C5H12
IUPAC NOMENCLATURE
IUPAC International Union of Pure
and Applied Chemistry
Branched - chain alkanes are named
according to the following rules:
CH3CH2CH2CH2CHCH3
CH2
CH3
Parent name : heptane
CH3CH2CH2CH2CHCH3
CH3
substituent
CH3CH2CH2CH2CH CH3
|
2 CH2
|
1 CH3
substituent
Examples:
6
CH3CH2CH2CH2CHCH3
CH3
2-methylhexane
Substituent
-methyl at C-2
Substituent
7
-methyl at C-3
CH3CH2CH2CH2CH CH3
|
2 CH
2
|
1 CH
3
3-methylheptane
name
methyl
ethyl
propyl
isopropyl
butane
butyl
substituent
CH3
CH2CH3
CH2CH2CH3
CHCH3
CH3
CH2CH2CH2CH3
isobutyl
CH2CHCH3
CH3
sec-butyl
tert-butyl
CHCH2CH3
CH3
CH3
CCH3
neopentyl
CH3
CH3
CH2CCH3
CH3
cyclopropyl
cyclobutyl
phenyl
C6H5 or
benzyl
CH2
name
substituent
Bromo
-Br
Chloro
-Cl
Flouro
-F
Iodo
-I
Hydroxyl
-OH
Amino
-NH2
Cyano
-CN
Nitro
-NO2
Example:
1
CH3CHCH2CHCH2CH3
|
|
CH3
CH2
|
CH3
4-ethyl-2-methylhexane
2,3-dimethylbutane
4
4
3
3
2
2
1
1
CH3CH2-CH CH CH CHCH3
|
|
|
|
CH3 5 CH2 CH3 CH3
|
6
CH2
|
7
CH3
2,3,5-trimethyl-4-propylheptane
(four substituents)
4-sec-butyl-2,3-dimethylheptane
(three substituents)
CH3CHCH2CH CHCH3
1
2
3
4
5
6
|
|
|
CH3
CH3 CH3
2,3,5-trimethylhexane
(NOT 2,4,5-trimethylhexane)
CYCLOALKANES
Cycloalkanes alkanes which carbon atoms are joined
in rings.
Cycloalkanes are known as saturated hydrocarbon,
because it has the maximum number of bonded
hydrogen ( only has single bonds).
General formula:
CnH2n where n = 3, 4, 5,
NOMENCLATURE OF
CYCLOALKANES
Cycloalkanes with only one ring are named with
the prefix cyclo- to the names of the alkanes
(contain the same number of carbon atoms)
cyclopropane
C4H8
cyclobutane
C5H10
cyclopentane
CH3
Methylcyclohexane
and
number in the direction that gives the next
substituent the lowest number possible.
Examples:
CH3
3
1
5
CH2CH3
1-ethyl-2-methylcyclohexane
NOT
1-ethyl-6-methylcyclohexane
Cl
Cl
1,3-dichlorocyclopentane
(NOT 1,5-dichlorocyclopentane)
Locants
Example:
2
Cl
3
2
4
1
5
6
CH2CH3
CH3
chloro 1
ethyl 3
methyl 4
1-chloro-3-ethyl-4-methylcyclohexane
4- chloro-2-ethyl-1-methylcyclohexane
H3C
CH2CH3
CH3
1-ethyl-1,3-dimethylcyclopentane
(NOT 3-ethyl-1,3-dimethylcyclopentane)
or
when more than one ring system is
attached to a single chain, then it is
appropriate to name the compounds as
cycloalkylalkane.
Number of C at
linear chain
Number of C at ring
3
2
1,3-dicyclohexylpropane
Examples:
CH2CH2CH2CH2CH3
1-cyclobutylpentane
Boiling
Point
Physical
state
Solubility
Physical state
At room temperature (25oC) and atmospheric
pressure (1 atm), for unbranched alkanes,
C1 C4 : gases
C5 C17 : liquids
C18 - more : solids
Boiling points
The boiling points of the straight alkanes show a
regular increase with increasing molecular
weight.
Branching of the alkanes chain, lower the boiling
point.
Mr boiling point
Mr boiling point
Chain branching :
makes a molecule more compact
Surface area reduces
The strength of the London dispersion forces
reduce
Lower boiling points.
Isomeric Alkanes
Have different boiling point due to branching
Pentane
2-methylbutane
2,2dimethylpropane
CH3CH2CH2CH2CH3
CH3CHCH2CH
CH3
CH3
CH3CCH3
CH3
9oC
37oC
28.5oC
butane
CH3CH2CH2CH3
CH3CHCH3
CH3CHCH3
2-methylpropane
CH3
CH3
In butane the C atoms are arranged in a
single chain, but 2-methylpropane is a
shorter chain with a branch
Name
Molecular structure
Boiling point
Cycloalkanes
The boiling points of cycloalkanes are 10oC
to 15oC higher than the corresponding straight
chain alkanes.
Cycloalkane Boiling point
alkane
Boiling
point
Cyclobutane
13oC
Butane
-0.5oC
Cyclopentane
49oC
Pentane
36..3oC
Solubility
CHEMICAL REACTION OF
ALKANES
Non-reactivity of alkanes
Reaction of alkanes
Combustion
Halogenation
Combustion of alkanes
y
y
CxHy+ x O2 x CO2 + H2O
4
2
+ Heat
Examples:
Combustion of alkane in excess oxygen
4H2O
Examples:
Combustion of alkane in limited oxygen
The
hv RX + HX
Examples:
i.
CH4 + Cl2
hv
CH3Cl + CH2Cl2
+ CHCl3 + CCl4
+ HCl
ii.
hv
CH3CH3 + Cl2 CH3CH2Cl + HCl
CH3
CH3
|
iii. CH3 CCH3 + Cl2
|
CH3
|
hv CH CCH Cl + HCl
3
2
|
CH3
CH3CH2CH2Br
iv.
CH3CH2CH3
hv
+ Br2
( minor)
+ CH3CHCH3
|
Br
( major)
+ HBr
Reaction mechanism
CH4 + Cl2
i.
hv CH3Cl + HCl
Cl Cl
hv
2Cl
H + Cl CH3 + HCl
H
3HC + Cl Cl_ CH3Cl + Cl
Cl2
Cl + CH3 CH3Cl
CH3 + CH3 CH3CH3
Example
CH3
C
H
CH2
CH3
CH3
CH3
CH3
CHBr
Increasing % yield
CH3
CH3
C
Br
CH2
CH3
Exercise
12.2
ALKENES
Unsaturated hydrocarbon
IUPAC Nomenclature
Step 1
Determine the parent name by
selecting the longest chain that
contains the double bond and change
the ending -ane in alkane to -ene.
Step 2
When the chain contains more than
three carbon atoms, a number is need
to indicate the location of the double
bond.
The chain is numbered starting from
the end closest to the double bond..
CH3CH2CH
CH CH2CH2CH2CH3
Step 3
Indicate the position of the substituent by the
number of the carbon atoms to which they
are attached.
CH3
H3 C
CH CH3
1
2
3
4
2-methyl-2-butene
(not 3-methyl-2-butene)
H3C
CH CH2 CH CH3
CH3
CH3
2,5-dimethyl-2-hexene
(not 2,5-dimethyl-4-hexene)
Step 4
H2C
CH CH
CH2
1,3-butadiene
1
H2C
CHCH
CHCH CHCH3
1,3,5-heptatriene
MORE
Step 5
In cycloalkenes :
Number the carbon atoms with a double
bond as 1 and 2, in the direction that gives
the substituent encountered first with a
small number.
CH3
1
5
2
4
1-methylcyclopentene
(not 2-methylcyclopentene)
1
6
CH3
CH3
3,5-dimethylcyclohexene
(not 4,6-dimethylcyclohexene)
MORE
Step 6
Two frequently encountered alkenyl
groups are vinyl group and allyl group.
RCH=CHR
alkene
CH2=CHvinyl group
-H
RCH=CHalkenyl
CH2=CHCH2allyl group
Step 7
cis / trans
Cl
C
H
Cl
C
H
cis-1,2-dichloroethene
Cl
C
H
H
C
Cl
trans-1,2-dichloroethene
2)
CH3
CH3
3)
4)
CH2CH3
CH3
5)
CH3CH=CHCH2C(CH3)2CH3
Preparation of alkenes
a) Dehydration of alcohols
b) Dehydrohalogenation of alkyl halide
OH
Dehydration of alcohols
Alcohols react with strong acids in the
presence of heat to form alkenes and water.
H2SO4 (conc.)
H2 O
Saytzeffs Rule
An elimination usually gives the most
stable alkene product, commonly the
most highly substituted alkene.
Examples
(1) CH3CH2OH
H2SO4 (conc.)
H2SO4 (conc.)
H2C CH2
H2C
H2O
CH CH3
H2O
H SO (conc.)
2
CH 3 CH=CHCH 3
(major product)
CH 2 =CHCH 2 CH 3
(minor product)
H 2O
Step 1:
Protonation of alcohol.
H
H3C C CH2CH3
:OH
..
H
+
:O H
H
H
H3C
C
+
: OH
H
CH 2 CH 3
:O
..
Step 2:
Formation of carbocation
H
H 3 C C CH 2 CH 3
+:OH
H
H3 C
H
+
C CH2 CH3
carbocation
H
+
:O
..
Step 3:
Formation of alkenes
H
H H H
+
H C C C CH3
b
:O H
..
H
C
H3C
H
+
C
CH 3
+
: O
stable alkenes
+
CH 2 =CHCH 2 CH 3
(minor product)
CH3OH
CH3
H2 SO4 (conc.)
CH3
H 3C
CH3
CH3
(major product)
CH
3
H C C CH CH
2
3
CH
3
(minor product)
Step 3:
Now the rearrangement occurs.
The less stable, secondary carbocation
rearrange to form more stable tertiary
carbocation.
CH
H C
3
CH
CH
CH H
3
H C
rearrangement
CH
CH H
3
2o carbocation
3o carbocation
(less stable)
(more stable)
CH
(a)
HC
2
(a)
3
CH CH
CH
H + CH3
H C C C CH3
H CH H
3
3
(minor product)
:O H
..
(b)
(b)
3
C CH
CH
3
(major product)
more stable alkene
The
The final
final step
step can
can occur
occur in
in two
two ways:
ways:
Try this!
CH H
3
H C C C CH
3
3
H OH
CH
3
H C C CH CH
3
3
(major product)
H2SO4 (conc)
CH
3
H C C CH CH
2
2 3
(minor product)
alcohol
KOH
reflux
C C
H X
HX
Examples:
(1)
Cl
H3C
CH CH2CH2CH3
H3C CH
CH CH2CH3
(major product)
KOH
alcohol
reflux
H2C CH CH2CH2CH3
(minor product)
(2)
H3C CH CH3
Br
KOH
alcohol
reflux
H2C
CH CH3
(3)
Br
+
CH
CH
3
KOH
alcohol
reflux
CH
CH
3
(minor product)
CH2
CH3
(major product)
(4)
CH3
CH3 H
C C CH3
CH3 Cl
CH2
CH3 H
C C CH3
CH3
2,3-dimethyl-1-butene
(minor product)
2 alkyl groups
+ KOH
CH3
alcohol
reflux
CH3
C C CH3
CH3
2,3-dimethyl-2-butene
( major product)
4 alkyl groups
Electrophilic Additions
Mechanism
H
H
C
C
H
slow
C
X
H
H
C
X
C H
fast
C H
Example:
i.
H3C
CH3
C
H3C
Cl
slow
CH3
CH3CH3
H3C
C
H
CH3
Cl
CH3CH3
H3C
C
H
CH3
Cl-
fast
CH3CH3
H3C
H Cl
CH3
C C
H2
Pt or Ni or Pd
C C
H H
Examples:
(1)
H3C
CH2
H2
Pt /Ni / Pd
CH3
CH3
(2)
H3C CH CH3
H2
Pt /Ni / Pd
X2
CH2Cl2
Example:
CH3
H3C C C CH3
CH2Cl2
Cl 2
H
Cl Cl
H3C
CH3H
CH3
Unsaturation test
C C
Br2
CH2Cl2
room temperature
C C
Br Br
rule
HX
C C
H X
Markovnikovs Rule:
In
i.
H H
H2C CH CH3
HBr
H C C CH3
H Br
ii.
Br
H3C C CH2
CH3
HBr
H3C C CH3
CH3
Mechanism
CH 3
CH 3
CH
CH 3
slow
H
Br
CH3
CH3
C
+
CH
30 Carbocation
CH3
+ Br -
CH3
CH3
C
+
CH
CH3
Br
fast
CH3
CH3
CH
Br
CH3
Example:
H2C CH CH3
HBr
ROOR
Br CH2CH2CH3
(1)
H3C
CH2C
CH2
HBr
H2 O 2
CH3
(2)
CH2
HBr
H2 O2
C C
X2
H2O
C C
X OH
X2 = Cl or Br
halohydrin
Example:
H
+ Br2 + H2O
C C
H
H H
H
H
Unsaturated test
H C C H
Br OH
2-bromobutanol
Example:
H 3C
CH2
Br 2
H2O
CH3
CH3H
H3 C
OH Br
1-bromo-2-methyl-2-propane
+
CH3
Br2
H2O
C C
H2O
H3O
C C
H OH
Example:
H3C
CH2
H3 O
H2O
CH3
OH
H3C
C
CH3
CH3
(1)
CH2
H2 O
H3 O
(2)
H2C
CH CH3
H2O
H3O
Mechanism
STEP 1
CH3
CH3
..
CH
CH3
O+
CH3
CH3
C
+
CH
H
CH3
STEP 2
CH3
C
+
CH
CH3
H2O
..
CH3
..
CH3
CH3
CH
O+
..
CH3
STEP 3
CH3
CH3
CH
O+
..
CH3
CH3
CH
OH
..
H2O
CH3
..
CH3
H3O+
..
H3 C
CH3
C
H3 C
CH3CH3
conc. H2 SO 4
H3 C
CH3
H OSO 3 H
alkyl hydrogen sulphate
CH3
CH3CH3
H2O
heat
H3 C
OH
CH3
Example:
H2C CH CH 3
OSO3H
conc.H2SO4
H3C CH CH2
H
H2O
heat
OH
H3 C
CH CH2
H
7 ) Oxidation of Alkenes
KMnO4
basic,cold,dilute
acidic,hot,concentrated
ozonolysis
i)
KMnO4
(purple)
OH OH
OH ,cold
MnO2
(brown precipitate)
Example:
-
H2C
CH2
+
H
KMnO4
H
OH OH
OH ,H2 O
cold
MnO2
CH3
(i) OH ,heat
KMnO4
(ii) H3O
CH3
O
H3C
O
CH3
H3C
CH3
2)
-
H2C
CH CH3
KMnO4
(i) OH ,heat
(ii) H3O
O
HO
CH3
CO2
H2 O
Example:
An unknown alkene with the formula C7H14
undergoes oxidation with hot basic potasium
permanganate solution to form propanoic acid
and butanoic acid. What is the structure of this
alkene?
C7 H14
KMnO4
O
H3C
CH2
(i) OH-,heat
(ii) H3 O
O
OH
CH2 C
H3C
CH2 OH
Answer:
O
H3C
CH2
O
CH2 C
H3C
CH2 OH
OH
propanoic acid
butanoic acid
H H
H3C
CH2C
CH2CH2CH3
3-heptene
Example
CH3CCH2CH2CH2CH2C OH
Deduce the structural formula for the unknown
alkene.
iii)
Ozonolysis of Alkenes
O3
O
ozonide
Ozonides:
very unstable compounds
Zn
H2 O,H
ozonide
H
C=O
O=C
R
Example:
CH3
H3C
(i) O3
CH CH3
(ii) Zn,H2O/H
CH3
H3C
CH3
Exercise
1.
Example
Exercise
1 awoke, as if by lightening;
this time, too, I spent the rest of
the night working out the
consequences of this
hypothesis
August Kekul
AROMATIC COMPOUNDS
14.1
Introduction to
aromatic Compounds
KEYWORDS
aromatic
resonance structure
Kekul structure
ortho meta para
Friedel-Craft acylation
electrophilic substitution
activating and
deactivating group
oxidation of
alkylbenzene
substitution of
toluene
DISCOVERY OF BENZENE
1825
Michael Faraday
(British)
1834
heat
C6H6 + CaCO3
gum benzoin
benzin
benjoin
(French)
benzoin
Luban Jawi
(Arabic)
1866
AROMATIC COMPOUNDS
In earlier time, compounds are called
aromatic because of their pleasant odours.
AROMATIC COMPOUNDS
Aromatic compound is a cyclic conjugated
molecule or ion that is stabilized by electron
delocalisation.
it is characterised by substitution reactions.
KEKULS STRUCTURE
Kekule was the first to formulate a
reasonable representation of benzene
H
H
H C C
C
H
or
H
The Kekule structure suggests alternating double
and single carbon-carbon bonds
RESONANCE STRUCTURE
Benzene is actually a resonance hybrid of the
two Kekul structures.
equivalent to
resonance hybrid
ly
e
t
e
l
p
Com
ted
a
g
u
j
n
co
Planar
Conta
in par
ticula
numb
r
e r of
electr
on
obe
ys H
Rule ckels
Benzene
aromatic
Benzene is aromatic because:
contains 6 electrons
(obeys Hckels Rule)
[4n+2] = [4(1) + 2]
= 6 electrons
AROMATIC COMPOUNDS
14.2
Nomenclature of benzene
and its derivatives
EXAMPLE:
CH3
Common: toluene
IUPAC:
methylbenzene
fluorobenzene
Br
chlorobenzene
NO2
nitrobenzene
bromobenzene
CH2CH3
ethylbenzene
toluene
COOH
benzoic acid
OH
NH2
phenol
aniline
CHO
benzaldehyde
DISUBSTITUTED BENZENE
Two Same Substituents
2
3
3
4
Br
Br
1,2dibromobenzene
1,4dibromobenzene
or
or
1,3dibromobenzene
odibromobenzene
pdibromobenzene
or
mdibromobenzene
NO2
1
NO2
NO2
1
2
3
NO2
1,2dinitrobenzene
or
odinitrobenzene
NO2
1
1,3dinitrobenzene
or
mdinitrobenzene
2
3
4
NO2
1,4dinitrobenzene
or
pdinitrobenzene
DISUBSTITUTED BENZENE
Two Different Substituents
COOH
1
COOH
1
2
4
NO2
NO2
2nitrobenzoic acid
4nitrobenzoic acid
or
or
3nitrobenzoic acid
onitrobenzoic acid
pnitrobenzoic acid
or
mnitrobenzoic acid
Br
1
Br
3
4
Br
1,2,4tribromobenzene
Br
I
2bromo1chloro3iodobenzene
COOH
2
NO2
HO
NO2
2,4dinitrophenol
Br 4
OH
3,5dihydroxybenzoic acid
3
CH3
CH3
4bromo1,2dimethylbenzene
Br 4
CH3
CH3
4bromo1,2dimethylbenzene
correct
4bromoodimethylbenzene
o, m and p naming system is used
for arenes with 2 substituents only!
14.2-11
PHENYL GROUP
Benzene ring as substituent.
If alkyl substituent is larger than the ring
(more than 6 C), the compound is named as
phenyl-substituted alkane.
1 CH2
3
2 CHCH
2CH2CH2CH2CH3
2phenylheptane
Phenyl = C6H5 = Ph
14.2-12
CH2C
3 4
CCH3
1phenyl2butene
CH2CH2OH
2phenylethanol
14.2-13
BENZYL GROUP
CH2
phenyl group
CH2Br
benzyl bromide
benzyl group
CH2OH
benzyl alcohol
AROMATIC COMPOUNDS
14.3
14.3-01
BENZENE
KMnO4 / H2O
H2 / Ni
no addition of Br2
(no decolorization)
no oxidation
(no decolorization)
slow addition at high
temperature and pressure
14.3-03
REACTION OF ARENES
Involves the benzene ring itself
Electrophilic aromatic substitution
+ Br2
benzene
Br
FeBr3
bromobenzene
COOH
benzoic acid
14.3-04
ELECTROPHILIC SUBSTITUTION
Most characteristic reaction of benzene.
A H atom is replaced by an electrophile.
E
+
E+
electrophile
H+
14.3-05
X2, FeX3
(X = Cl Br)
X
+ HX
HONO2
NO2
+ H2O
H2SO4
RCl , AlCl3
(R can rearrange)
O
RCCl , AlCl3
halogenation
nitration
R
+ HCl
Friedel-Crafts
Alkylation
O
CR
+ HCl
Friedel-Crafts
Acylation
14.3-07
GENERAL MECHANISM
Formation of arenium ion
STEP 1
H
H
E+
H
H
H
E
H
H
H
H
E
H
H
H
H arenium ion
H
H
14.3-08
ARENIUM ION
+
E+
benzene ring
E
H
arenium ion
Loss of
STEP 2
H
H
E
H
14.3-09
H+
H
H
E+
6 electrons
E
H
4 electrons
H+
E
6 electrons
14.3-10
STEP 1
+ E+
arenium ion
E
STEP 2
E
H
+ H+
14.3-11
HALOGENATION
Reactants: benzene and halogens (Cl2 or Br2).
Conditions:
Lewis acid such as FeCl3 and FeBr3
no reaction
(decolorization not observed)
+ Br2
+ Br2
FeBr3
Br
+ HBr
bromobenzene
14.2-13
MECHANISM
STEP 1
Formation of Br+
+
BrBr
STEP 2
BrBrFeBr3
complex
+ FeBr3
Br+
+ FeBr4
Br
+ Br+
STEP 3
Loss of H+
Br
FeBr4
Br
+ HBr + FeBr3
14.3-14
14.3-15
NITRATION
Reactants: benzene and concd. HNO3.
Conditions:
Concd. H2SO4
NO2
HNO3
H2SO4
nitrobenzene
+ H+
+ HSO4
12.5-49
MECHANISM
STEP 1
..
..
H-O-NO2 +
H-OSO3H
+-NO
H-O
+
HSO
.. 2
4
H2O + NO2+
nitronium ion
STEP 2
STEP 3
Loss of H+
HSO4
NO2
NO2
+ H2SO4
12.5-51
FRIEDELCRAFT ALKYLATION
Reactants: benzene and haloalkane.
Conditions:
Catalyst: Lewis acid such as AlCl3.
+ RX
AlCl3
R
+ HCl
alkylbenzene
Alkylation = transfer an
alkyl group to benzene
12.5-52
12.5-53
EXAMPLE:
Cl
CH(CH3)2
AlCl3
+ CH3CHCH3
2chloropropane
+ HCl
isopropylbenzene
+ (CH3)3CCl
AlCl3
C(CH3)3
+ HCl
2chloro2methylpropane
tertbutylbenzene
12.5-54
MECHANISM
Formation of carbocation
(CH3)2CHCl: +
AlCl3
+ (CH3)2CHClAlCl3
: :
: :
STEP 1
(CH3)2CH+
+ AlCl4
carbocation
STEP 2
CH(CH3)2
+
+CH(CH )
3 2
Loss of H+
STEP 3
AlCl4
CH(CH3)2
CH(CH3)2
+ HCl
12.5-55
OTHER FACTS ABOUT
FRIEDELCRAFT ALKYLATION
35%
CH3CH2CH2CH2Cl
AlCl3
butylbenzene
CH3
CHCH2CH3
secbutylbenzene
Rearrangement:
H
65%
CH3CH2CHCH2
1o carbocation
CH3CH2CHCH3
2o carbocation
12.5-56
FRIEDELCRAFT ACYLATION
Reactants: benzene and acid chloride.
Product: ketone.
Conditions:
Catalyst: Lewis acid such as AlCl3.
EXAMPLE:
O
O
+
CH3CCl
AlCl3
CCH3
acetyl chloride
acetophenone
+ HCl
12.5-57
ACYL GROUP
O
RC
acyl group
EXAMPLE:
O
O
CH3C
acetyl group
C
benzoyl group
Acylation = transfer an
acyl group to benzene
12.5-59
MECHANISM
Formation of acylium ion
STEP 1
:O:
AlCl3
RCClAlCl3
: :
RCCl
:O:
RC+O
RCO+
acylium ion
+ AlCl4
STEP 2
C=O
+ RC+O
STEP 3
Loss of H+
R
C=O
AlCl4
R
CO
+ HCl
12.5-61
SUBSTITUENT EFFECT
But, what would happen if we were to carry out a reaction
on aromatic ring that already has a substituent?
12.5-62
EFFECT ON REACTIVITY
Activating groups:
Substituents that activate the ring,
making it more reactive than benzene.
Deactivating groups:
Substituents that deactivate the ring,
making it less reactive than benzene.
EXAMPLE:
relative rate
of nitration
NO2
6 x 108
Cl
0.033
reactivity
H
1
OH
1000
12.5-63
EFFECT ON ORIENTATION
Orthopara directors
Tend to direct the incoming group into
ortho and para positions.
Meta directors
Tend to direct the incoming group into
meta position.
EXAMPLE:
CH3
HNO3
H2SO4
ortho-para director
CH3
CH3
NO2
+
+
CH3
NO2
(59%)
(37%)
NO2
(4%)
12.5-64
CLASSIFICATION OF SUBSTITUENTS
ortho , para directing
activators
ORTHO , PARA
DIRECTING ACTIVATORS
12.5-65
Increasing activation
NH2
NHR NR2
OH
OR
General structure:
R or Z
NHCOR
R
12.5-66
EXAMPLE:
CH2CH3
CH2CH3
CH2CH3
Br
Br2
FeBr3
ethylbenzene
(38%)
(62%)
Br
12.5-67
ORTHO , PARA
DIRECTING DEACTIVATORS
Br
Cl
General structure
(halogens)
12.5-68
EXAMPLE:
Cl
Cl
Cl
NO2
HNO3
H2SO4
chlorobenzene
(35%)
(64%)
NO2
12.5-69
General structure:
Y (+ or )
12.5-69
EXAMPLE:
NO2
NO2
HNO3
H2SO4
NO2
nitrobenzene
(93%)
12.5-70
INDUCTIVE EFFECT
Due to:
Electronegativity of the atoms in the
substituent.
Polarisability of the substituent.
EXAMPLE:
Cl
Cl
electronwithdrawing
CH3
CH3
electrondonating
12.5-71
Activating Groups
Release electrons to the ring
Stabilise arenium ion
CH3
NO2
Form faster
Deactivating Groups
Withdraw electrons from the ring
Destabilise arenium ion
Form slower
Cl
NO2
12.5-72
EXAMPLE:
CF3
CH3
(trifluoromethyl)benzene
benzene
toluene
NO2
NO2
+
CF3 withdraws e-,
arenium ion less stable
ring less reactive
CH3
NO2
+
CH3 releases e-,
arenium ion more stable
ring more reactive
12.5-75
CH(CH3)2
12.5-76
EXAMPLE:
CH3
COOH
KMnO4
heat
toluene
O2N
benzoic acid
CH3
Na2Cr2O7
heat
pnitrotoluene
CH3
CH(CH3)2
isopropyl toluene
O2N
COOH
pnitrobenzoic acid
KMnO4
heat
HOOC
COOH
terepththalic acid
12.5-77
CH3
CH(CH3)2
KMnO4
heat
HOOC
COOH
CH3
C(CH3)3
KMnO4
heat
HOOC
C(CH3)3
12.5-78
HALOGENATION OF TOLUENE
Free radical substitution reaction
Take place at high temperature or in the
presence of uv light.
Mechanism: freeradical substitution
Cl or Br replaces H atom of alkyl group
EXAMPLE:
CH3
toluene
(dichloromethyl)benzene
CH2Cl
CHCl2
Cl2
Cl2
Cl2
heat or
light
heat or
light
heat or
light
benzyl chloride
CCl3
(trichloromethyl)benzene
HALOGENATION OF TOLUENE
Electrophilic aromatic substitution reaction
CH3
CH3
CH3
Br2
Br2
FeBr3
toluene
Br2
CH2
12.5-79
benzylic
radical
CARCINOGENIC EFFECT
12.5-34
CH3
benzene
toluene
12.5-35
12.5-36
benzo[a]pyrene
Benzo[a]pyrene is found in cigarette smoke, automobile
exhaust, and the fumes from charcoal grills.
When ingested or inhaled, it oxidised to carcinogenic
products.
12.5-21
12.5-20
12.5-22
12.5-19
END OF
SLIDE SHOW
CHAPTER 15
HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006
15.1 : Introduction
Haloalkanes or alkyl halides
General formula :
bonded
R-X
or CnH2n+1X (acyclic)
or CnH2n-1X (cyclic)
R CH 2 X
R
R CH X
Classification
methyl halide
- halogen is bonded
methyl group
to
General Formula
Classification
R C X
R
Aryl halide
- halogen is bonded to aromatic
ring
CH 2 X
Example :
Classify the following haloalkanes :
No.
Haloalkanes
Classification
i.
CH 3 CH 2 Br
10
ii.
CH 3 CH (Cl)CH 3
20
iii.
(CH 3 ) 3 C(Br)
30
H3C
iv.
Cl
30
5
substituents.
Locate and number the parent chain from the direction
Example :
i.
CH 3 CHCH 2 CH 3
Br
2-bromobutane
ii.
Cl
BrCH 2 CH 2 CHCHCH 2 CH 3
CH 3
1-bromo-3-chloro-4-methylhexane
7
Example :
iii.
CH 2 CH 2 F
CH 3 CH 2 CH 2 CHCH 2 CH 2 CH 3
4-(2-flouroethyl)heptane
iv.
H3C
CH 3
Cl
2-chloro-1,1-dimethylcyclopentane
Example :
v.
Br
4-bromocyclohexene
vi.
CH 2 Cl
vii.
CH 3
Cl
(chloromethyl)benzene
2-chlorotoluene
9
electrophilic
site
undergo
nucleophilic
substitution
reactions in which the halogen atom is replaced by a
nucleophile.
R _N u
_
X:
11
R_ X + NaOH
H2 O
R_ OH + NaX
Example :
CH3
H2 O
_
_
CH3 C Br + NaOH
CH3
CH3
CH3 _ C _OH + NaBr
CH3
12
_
_
R X + CN
alcohol
reflux
R_ CN
+ X
Example :
CH 3 CH 2 Br + KCN
alcohol
reflux
CH 3 CH 2 CN
+ KBr
13
R_ X
NH 3
_
+
RNH 3 X
NH 3
_
_
+
R N H2 + NH 4 X
(amine)
Example :
CH 3 CH 2 Cl + excess NH 3
_
+
CH 3 CH 2 NH 2 + NH 4 Cl
14
15.2.2 :
Mechanisms of Nucleophilic
Substitution Reaction
They are 2 important mechanisms for the substitution
reaction:
(A). Unimolecular Nucleophilic Substitution
(SN1)
Reaction
Reaction
15
Reaction
stabilities of carbocations.
Relative reactivities of haloalkanes in an SN1 reaction :
concentration of nucleophile.
The rate depends only on the concentration of the
17
R
R_ C _ X
s low
R
3o alkyl halide
R
_
_
R C+ + X
R
carbocation
halide ion
R
_
_
R C + + N u:
R
fas t
R
R_ C _ N u
R
18
Example 1 :
CH 3
CH 3 _ C _ OH + HBr
CH 3
SN1 mechanism :
s low
CH 3
CH 3 _ C +
CH 3
+ Br
_
19
CH 3
CH 3 _ C +
fa
s
t
H2O
CH 3
CH 3
H
_
_
CH 3 C O
+ H
CH 3
CH 3
H
_
_
CH 3 C O
+ H
CH 3
H2O
CH 3
CH 3 _ C _ OH + H 3 O +
CH 3
20
Example 2 :
CH3
CH3 _ C _CH2CH3 + NaBr
OH
SN1 Mechanism :
s low
CH 3
_
_
_
CH 3 C CH 2 + Br
+
CH 3
21
Rearrangement :
CH 3
CH 3 _ C _ CH 2
+
CH 3
1,2-meth yl s hift
CH 3
CH 3 _ C _ CH 2
+
CH 3
+ OH
fas t
CH 3
CH 3 _ C _ CH 2 CH 3
OH
22
KCN
NaOH/H2O
excess NH3
23
Substitution
(steric effect).
Steric effect
General Mechanism :
R
Nu:-
C X
H
R
slow
Nu C X
H H
transition state
fast Nu C
+ X27
28
Example 3 :
SN2 Mechanism :
CH3
CH3
:OHH
C Br
H
slow
OH C Br
H H
fast
CH3
OH C
H
+ Br-
transition state
29
SN2
A two-step mechanism
A one-step mechanism
A unimolecular
ratedetermining step
Second order :
rate = k [RX] [Nu]
A bimolecular
ratedetermining step
First order :
rate = k [RX]
Strong nucleophile
Weak nucleophile
Carbocation rearrangement
Reactivity order :
3o > 2o > 1o
No carbocation
rearrangement
Reactivity order :
methyl > 1o > 2o
30
H
_C_C_
_
C C
base
alkene
:B
X
haloalkane
31
Example :
Br
i.
CH 3 CHCHCH 3
CH 3 CH 2 ON a
CH 3 CH 2 OH
CH 3 C CHCH 3
CH 3
CH 3
major
+
CH 3 CHC CH 2
CH 3
minor
ii.
Br
CH 3
CH 3 CH 2 ON a
CH 3
CH 2
+
CH 3 CH 2 OH
major
minor
32
Mg
ether
R-MgX
Grignard Reagent
(
alkylmagnesium halide)
Example :
i. CH 3 CH 2 CH 2 Br + Mg ether CH 3 CH 2 CH 2 MgBr
ii.
Cl + Mg
ether
MgCl
33
Synthesis of alkane
The Grignard reagent is hydrolyzed to an
alkane when warmed with H2O.
RMgX + H 2 O
H+
R-H + Mg(OH)X
34
Example :
+
H
i. CH 3 CH 2 MgBr + H 2 O
CH 3 CH 3
+ Mg(OH)Br
ii.
CH 3 CH-MgBr + H 2 O
H+
CH 3 CH 2 CH 3
+ Mg(OH)Br
CH 3
iii.
CH 2 MgCl
H 2 O/H +
CH 3
+ Mg(OH)Cl
35
(ii).
Synthesis of 1o alcohol
Methanal reacts with the Grignard reagent,
followed by the hydrolysis produces primary
alcohol.
H
O
R-MgX + H-C-H
R-C-OMgX
H
H 2 O,H +
H
R-C-OH
H
Mg(OH)X
36
Example :
i.
O
CH 3 MgBr + H-C-H
H 3 O+
H
CH 3 -C-OH
+ Mg(OH)Br
ii.
MgBr
O
+ H -C-H
H 3 O+
CH 2 OH
+ Mg(OH)Br
37
(iii).
Synthesis of 2o alcohol
Grignard reagent reacts
produce secondary alcohol.
with
aldehydes
to
R'
O
R-MgX + H-C-R'
R-C-OMgX
H
H 2 O,H +
R'
R-C-OH
H
+ Mg(OH)X
38
Example :
O
CH 3 CH 2 MgBr + CH 3 CH 2 -C-H
i.
H 2 O/H +
H
CH 3 CH 2 -C-CH 2 CH 3 + Mg(OH)Br
OH
ii.
MgCl
O
+ CH 3- C-H
CH 3
H 2 O/H +
C-OH
H
+ Mg(OH )Cl
39
(iv).
Synthesis of 3o alcohol
produce
R'
O
R-MgX + R'-C-R"
R-C-OMgX
R"
H 2 O,H +
R'
R-C-OH
R"
+ Mg(OH)X
40
Example :
i.
CH 3 CH 2 MgBr + CH 3 -C-CH 3
H 2 O/H +
CH 3
CH 3 CH 2 -C-CH 3 + Mg(OH)Br
OH
ii.
MgCl
CH 3
O
+ CH 3- C-CH 3
H 3 O+
C-OH
CH 3
+ Mg(OH )Cl
41
(v).
O
RMgX + O C O
O
R-C-O-MgX + H 2 O
H+
R-C-O-MgX
O
R-C-OH + Mg(OH)X
42
Example :
O
CH 3 CH 2Mg I + CO 2
O
CH 3 CH 2- C-O-MgI + H 2 O
CH 3 CH 2- C-O-MgI
H+
O
CH 3 CH 2 COH + Mg(OH)I
43
dry ether
RR + 2NaX
Example:
2CH3CH2Br + 2Na CH3CH2CH2CH3 + 2NaBr
44
ii.
Example:
CH3CH2Br + CH3Br + 6Na CH3CH2CH2CH3
+ CH3CH2CH3
+ CH3CH3 + 6NaBr
45
Uses
CCl4
(carbon tetrachloride)
CHCl3
(chloroform)
CF2Cl2 , Freon-12
(dichlorodifluoromethane)
CFC
(chloroflourocarbons)
DDT
(DichloroDiphenylTrichloroethane)
HYDROXY COMPOUNDS
(ALCOHOLS)
Click me
for intro!
INTRODUCTION
INTRODUCTION
OH
CH2-OH
CH3CH2-OH
INTRODUCTION
OH
OH
OH
CH3
Br
CLASSIFICATION
10 Alcohols
R-CH2-OH
20 Alcohols
R
R-CH-OH
30 Alcohols
R
R-C-OH
R
5
NOMENCLATURE
Structure
General name
IUPAC name
CH3-OH
methyl alcohol
methanol
CH3CH2-OH
ethyl alcohol
ethanol
CH3CH(OH)CH3
isopropyl alcohol
2-propanol
OH
cyclohexyl
alcohol
cyclohexanol
CH3
CH3CCH2CH2CH3
OH
2-methyl-2-pentanol
2o
3o
CH3
HO-CHCH2CH3
CH3CH2CH2-OH
sec-butyl alcohol
2-butanol
n-propyl alcohol
1-propanol
2o
1o
Naming Alcohols
10
OH
OH
OH
CH3
CH2CH3
3-ethylphenol
Br
3-bromophenol
2-methylphenol
11
General name
IUPAC name
ethylene glycol
1,2-ethanediol
propylene glycol
1,2-propanediol
trimethylene
glycol
glycerol
1,3-propanediol
1,2,3-propanetriol
12
OH
OH
OH
OH
OH
1,4-benzenediol
(hydroquinone)
OH
1,3-benzenediol
(resorcinol)
1,2-benzenediol
(catechol)
13
EXCERCISE
1. Name the following compounds using IUPAC nomenclature
(a)
(b)
-CH2CH(CH3)CH2-OH
-OH
NO2
(b)
-OH
Br
14
PHYSICAL PROPERTIES
15
PHYSICAL PROPERTIES
No. of OH , b.p.
b.p. ROH > alkane & RX because of Hbonding
b.p. ROH straight chain > ROH branch
b.p. 1o ROH > 2o ROH > 3o ROH
16
PHYSICAL PROPERTIES
(ii)
Boiling point
As molecular weight increase, van der Waals
forces increase, boiling point will increase too.
O
-
H
R
O
-
Hydrophilic area
OH
H
H
Hydrogen
bonding
Hydrophobic area
19
20
2-nitrophenol
H
- O
O + O
N
N
+
Intramolecular H-bonding
O +
- H
O
H
Intermolecular H-bonding
21
22
23
O -
H
release proton
+ H+
Phenoxide ion
24
O
-
O-
25
Example:
OH
CH2CH2-OH
CH2-OH
OH
acidity increase
26
Example:
COOH
OH
>
> CH CH -OH
3
Na2CO3
KOH
K, Na
NaHCO3
NaOH
NaH
Weak bases
Strong bases
ACIDITY
DECREASE
EXCERCISE
1. Arrange the following compounds in the order of increasing
boiling point. Explain your answer.
1,2-ethanediol , n-butane , 1-propanol , 1,3-propanediol
2. Predict which of the compound is more soluble in water.
Briefly explain your answer.
(a) propane & 1-propanol
(b) 1-propanol & 1,2-propanediol
(c) 2-propanol & 2-pentanol
28
PREPARATION OF ALCOHOLS
1. Fermentation of carbohydrate
2CH3CH2OH + 2CO2
29
PREPARATION OF ALCOHOLS
2.Hydration of Alkenes
follows Markovnikovs rule
Example:CH3CH=CH2
H2O / H2SO4
CH3CH-CH3
OH
30
PREPARATION OF ALCOHOLS
Mechanism
CH3CH=CH2 + H+
CH3CH-CH3 2o carbonium
+
OH
CH3CH-CH3
OH
31
PREPARATION OF ALCOHOLS
3. Hydrolysis of Haloalkanes
RX + OH- (aq)
CH2Cl
ROH + X-
CH2OH
+ NaOH(aq)
32
PREPARATION OF ALCOHOLS
4. Addition of Grignard reagent to
carbonyl compounds
33
PREPARATION OF ALCOHOLS
(a) Formation of 1o alcohols (Grignard reagent + methanal)
CH3CH2-MgCl + H2C=O
CH3CH2CH2-OMgCl
methanal
H3O+
1o Alcohol
CH3CH2CH2-OH
+ Mg(OH)Cl
34
PREPARATION OF ALCOHOLS
(b) Formation of 2o alcohols (Grignard reagent + aldehyde)
CH3
CH3
CH3CH2-MgCl + HC=O
CH3CH2CH-OMgCl
ethanal
H3O+
CH3
2o Alcohol
CH3CH2CH-OH
+ Mg(OH)Cl
35
PREPARATION OF ALCOHOLS
(c) Formation of 3o alcohol (Grignard reagent + ketone)
O-MgCl
O
CH3-MgCl + CH3-C-CH3
propanone
CH3-C-CH3
CH3
H3O+
O-H
3o Alcohol
CH3-C-CH3 + Mg(OH)Cl
CH3
36
EXCERCISE
1. Write the chemical equation for the following reaction:
i.
-C-H
CH3
-CH=CH-CH3
H2O / H+
B + C
37
ALCOHOL REACTIONS
(a) As an acid
In an aqueous solution alcohol reacts as a very weak acid
ROH + H2O
RO- + H3O+
CH3CH2O-Na+ + 1/2H2
38
ALCOHOL REACTIONS
(a) As a base
With the presence of lone pair of e- at the O atom,
alcohol can accept proton from an acid
CH3CH2-O-H
+ HA
CH3CH2O+-H
+ A-
39
ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with carboxylic acid under reflux & is
catalysed by mineral acids (H2SO4 or HCl)
General reaction:O
H+,
R-C-OH + R-OH
acid
alcohol
R-C-OR + H-O-H
ester
water
40
ALCOHOL REACTIONS
(1) Esterification
Example:O
H+,
CH3C-OH + CH3-OH
ethanoic acid
methanol
CH3C-OCH3 + H-O-H
methyl ethanoate
41
ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with acyl chloride to form ester
O
base
CH3C-Cl + CH3-OH
ethanoil chloride
methanol
CH3C-OCH3 + HCl
methyl ethanoate
42
ALCOHOL REACTIONS
(2) Dehydration of alcohol
Involve formation of carbocation
Possible of rearrangement
CH3CH2CH2OH
propanol
H2SO4(con.)
1800C
CH3CH=CH2
propene
43
ALCOHOL REACTIONS
(3) Formation of haloalkane
ROH reacts with HX to form RX
The reaction rates are in the order
HI > HBr > HCl (HF non-reactive)
Reactivity of alcohols
3o ROH > 2o ROH > 1o ROH > phenol
44
ALCOHOL REACTIONS
Example:-
ROH + HX
CH3CH2CH2OH + HBr
RX + H2O
CH3CH2CH2Br + H2O
45
ALCOHOL REACTIONS
(3) Formation of haloalkane
ROH reacts with PX3, PX5 , SOCl2
General reaction:
(i) 3ROH + PX3
3RX + H3PO3
(iii)ROH + SOCl2
46
ALCOHOL REACTIONS
(4) Oxidation of alcohols
47
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
1o R-OH can be oxidised to give an aldehyde.
Further oxidation would give a carboxylic acid
RCH2OH
1o alcohol
[O]
O
RC-H
aldehyde
[O]
O
RC-OH
carboxylic acid
48
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
Example:-
CH3CH2OH
K2Cr2O7
/H+
O
CH3C-H
K2Cr2O7/H+
O
CH3C-OH + Cr3+
green
orange
49
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
Sarett-Collins reagent is a special oxidation
agent to change a 1o alcohol to an aldehyde
CrO3 is added to excess pyridine to form
pyridinium chlorochromate (PCC)
CH3CH2CH2OH + PCC
propanol
O
CH3CH2C-H
propanal
50
ALCOHOL REACTIONS
(4) Oxidation of 2o alcohol
form ketone which cannot be oxidised further
under normal conditions
R
RCH-OH
2o alcohol
[O]
R
RC=O + H2O
ketone
CH3
CH3
+
KMnO4/H
CH3CH-OH
CH3C=O + H2O
2-propanol
propanone
51
ALCOHOL REACTIONS
(4) Oxidation of 3o alcohol
Does not undergo oxidation under normal
condition
R
R-C-OH
[O]
no reaction
R
3o alcohol
52
Lucas test
53
OBSERVATIONS :
Example:
CH2OH
HCl / ZnCl2
HCl / ZnCl2
Turn cloudy
within 5 minute
OH
54
CH3
OH
HCl / ZnCl2
OBSERVATIONS :
Turn cloudy
immediately
55
Haloform Reaction
X2 , H+
OH-
HCX 3 + H
C OH
O
H
CH 3 C R
OH
X2 , H+
OH-
HCX 3 + R
C OH
O
56
IODOFORM TEST
OH
57
PHENOL
Manufacture of phenol by Cumene process
(a) Friedel-Crafts reaction
CH3-CH-CH3
+ CH3CH=CH2
AlCl3
Isopropylbenzene
(cumene)
58
PHENOL
(b) Oxidation of Cumene
CH3-CH-CH3
+ O2
O -OH
CH3-C-CH3
1200C
Cumene
hydroperoxide
H2SO4
O
-OH + CH3CCH3
CH3
59
Phenol reactions
1. Reaction at functional group -OH
(a) Reaction with Na
O-Na+
OH
+ Na
+ H2
60
Phenol reactions
1. Reaction at functional group -OH
(b) Reaction with NaOH
O-Na+
OH
+ NaOH
CH3CH2OH + NaOH
+ H2O
no reaction
61
Phenol reactions
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6tribromophenol will form
OH
OH
Br
Br
+ 3Br2 / H2O
+ 3HBr
Br
62
Phenol reactions
2. Electrophilic substitution reactions
(a) Bromination to get monobromination (catalyst:
FeBr3 or CS2)
OH
OH
+ Br2
OH
Br
CS2
50C
+ HBr
Br
63
Phenol reactions
2. Electrophilic substitution reactions
(b) Nitration
OH
OH
NO2
Dilute HNO3
Room temp.
OH
NO2
OH
O2N
NO2
Concentrated HNO3
Yellow
precipitate
NO2
64
Phenol reactions
3. Esterification
phenol is a weaker nucleophile than alcohol since
the lone pair e- of O atom are delocalised to the
benzene ring
reacts with an acid derivative such as acid chloride
to form an ester
CH3
OH
O-C=O
Cl
+ CH3-C=O
+ Cl65
Phenol reactions
4. Identification test for phenols
phenol reacts with aqueous solution of iron (III)
chloride giving a light purple complex
OH
OH
+ FeCl3 (aq)
FeCl3
Purple
complex
66
EXERCISE 1
Suggest a chemical test to differentiate the following pairs of
compounds. State the reagents, observations and write
chemical equations involved.
(a) methanol from ethanol
(b) 2-methyl-1-propanol from 2-methyl-2-propanol
(c) cyclohexanol from cyclohexane
(d) phenol from benzyl alcohol
(e) o-methylphenol from 2-methylcyclohexanol
67
EXERCISE 2
Compound A (C4H10O) undergoes oxidation to form compound
B (C4H8O). Oxidation of B gives compound C (C4H8O2).
Reaction of A with hot concentrated sulphuric acid yields
compound D (C4H8). Hydration of D gives compound E
(C4H10O) which cannot be oxidised. A and E are isomeric.
Suggest the structure of A, B, C, D and E. Rasionalise your
answer.
68
Phenols in Medicine
OH
OH
CH2CH2CH2CH2CH2CH3
Phenol
Resorcinol
(antiseptic)
4-Hexylresorcinal
(antiseptic)
70
Derivatives of Phenol
71
17.0
CARBONYL COMPOUNDS:
ALDEHYDES AND KETONES
17.1 Introduction
Aldehydes and ketones are carbonyl compounds
O
Aldehyde
O
R C H
ketone
O
R C
17.2 Nomenclature
The longest continuous carbon chain with
-CHO group gives the parent name.
Aldehydes : the -e ending is replaced by al
Ketones : the e ending is replaced by one.
The chain is numbered in the direction that
provides the lower number for the functional
group.
Example
butanal
O
CH3CH2CH2C H
CH3
2-ethyl-4-methylpentanal
CH3CH CH2CH C H
CH2 CH3
CH3
3,5-dimethyl-2-hexanone
Structure
formula
Aldehyde
H2C=O
Ketone
IUPAC
nomenclature
Common name
Methanal
Formaldehyde
CH3CH=O
Ethanal
Acetaldehyde
CH3CH2CH=O
Propanal
Propionaldehyde
CH3CH2CH2CH=O
Butanal
Butyraldehyde
CH3COCH3
Propanone
Acetone
CH3CH2COCH3
2-butanone
CH3CH2CH2COCH3
2-pentanone
CH3CH2COCH2CH3
3-pentanone
Diethyl ketone
4
Example
i)
2- methylpentanal
O
CH3CH2CH2CH C H
CH3
ii) 3- hexanone
O
CH3CH2C CH2CH2CH3
iv) 3-ethylcyclopentanone
CH3 CH2
v) 3-cyclohexylpropanal
CH2 CH2 C H
O
a) Oxidation Alcohols
When 1o
alcohols
are oxidised using
pyridinium chlorochromate (PCC) in CH2Cl2,
aldehydes are formed.
Example
1.
H
CH3 C
OH
PCC
CH2Cl2
CH3 C
H
ethanol
ethanal
(alcohol 10)
(aldehyde)
CH3
2.
CH3 C
OH
H
2-propanol
KMnO4, H+
heat
CH3 C
CH3
propanone
(alcohol 20)
3.
CH3
CH3 C
OH
no reaction
CH3
2-methyl-2-propanol
(alcohol 30)
b) Ozonolysis of Alkenes
R1
C
R1
C
R2
O
i. O3
ii. H2O/Zn
R C
H + R1
ii. H2O/Zn
R C
O
i. O3
R2 + R1
R3
R3
Example:
1.
CH2 CH3
H 3C
C
H
i. O3
ii. H2O/Zn
2-pentene
10
2.
CH2CH3
CH3 C
i. O3
CH CH2 CH3
ii. H2O/Zn
3-methyl-3-hexene
3.
CH3
i. O3
ii. H2O/Zn
4-methylcyclopentene
11
OH
R C
C R 1 + H 2O
H2SO4
HgSO4
R C
CH R1
Enol
R C CH2 R1
Keto
Example:
H C
C H + H 2O
H2SO4
HgSO4
ethyne
H 3C C
C H + H 2O
propyne
H2SO4
HgSO4
12
+ CH3 C Cl
O
+ R
C O C
R'
AlCl3
13
CHO
CHCl2
2Cl2
H2O
uv
14
R1
aldehyde or ketone
(R or R1 may be H)
R
H
OH
C
O + Nu
R C
Nu
15
General Mechanism
The nucleophile attacks the partially positive
carbonyl group and breaking the carbonyl bond.
16
a)
OH
O + HCN
R C CN
H
cyanohydrins
OH
O + HCN
R1
R C CN
R1
NaCN
H2SO 4
HCN
NaHSO 4
17
Example:
CN
H C OH
CHO
NaCN
H2SO 4
Mechanism:
18
Exercises.
1.
O
H3C
NaCN
C H
H2SO 4
2.
O
H3C
NaCN
C CH3
H2SO 4
19
20
Grignard
reagents
react
with
carbonyl
H
CH3CH2CH2CH2MgX
+ HCOH
21
CH2CH2CH3
CH3 CH2MgX + HC O
H+
CH2CH3
CH3CH2CH2MgX + C O
H+
CH3
22
O
H
R + H2O
H+
HO
OH
R
O
R'
R + H2O
H+
HO
R'
OH
23
Example:
1.
O
H
H+
CH3 + H2O
ethanal
2.
O
H
H+
+ H2O
methanal
3.
O
CH3 CH2C
CH3 + H2O
H+
2-butanone
24
Mechanism :
O
H 3C
H+
CH3 + H2O
propanone
25
O
R
OH
H
R'OH
C OR'
H
hemiacetal
OH
R'
R''OH
OR''
R'
hemiketal
A hemiacetal or hemiketal in acidic medium
can reacts further to produce an acetal or
ketal.
OH
R
C OR'
H
hemiacetal
R''OH
OR''
C OR'
H
acetal
27
OH
R
OR'''
OR''
H
R'''OH
R'
hemiketal
OR''
R'
ketal
28
Example:
1.
H
CH3 CH2 CH2 C
O + CH3CH2CH2OH
HCl
2.
OCH2CH2CH3
CH3 CH2 CH2 C
OH + CH3CH2CH2OH
HCl
29
3.
CH3
CH3 CH2 C
+ CH3CH2CH2OH
HCl
4.
OCH2CH2CH3
CH3 CH2 C
OH + CH3CH2CH2OH
HCl
CH3
30
O + NaHSO3
+
Na
SO3H
OH
C
_
SO3
+
Na
Example:
1.
CH3
C
O + NaHSO3
31
2.
H
CH3 CH2 C O + NaHSO3
32
O + H2N-Z
aldehyde
or
ketone
H3O+
N-Z + H2O
Z = -H, -OH,
-NH2 ,etc.
Example:
33
R NH2
amine 10
H2N NH2
hidrazina
C O
C NR
C NNH2
imine
hydrazone
H2N OH
hidroxylamine
C NOH
H 2N
NH
C NNHC6H5
phenylhydrazine
phenylhydrazone
O
O
H2N NH C NH2
semicarbazide
H2N
NH
O2N
NO2
2,4-dinitrophenylhydrazine
oxime
C NNH C NH2
semicarbazone
C N
NH
O2 N
NO2
2,4-dinitrophenylhydrazone
34
(Bradys reagent)
35
a) Oxidation
Aldehydes are oxidized to carboxylic acid
while ketone are hardly oxidized.
Example :
O
CH3 (CH2)4 C H + K2Cr2O7
O
H+
CH3 (CH2)4 C OH
36
b) Reduction
Aldehydes are reduced to primary alcohols and
ketones to secondary alcohols.
OH
O
R
C H
aldehyde
H2, Ni
C H
H
alcohol 10
37
OH
O
R
C R1
H2, Pt
ketone
C R1
H
alcohol 20
Example:
1.
O
CH3 C H
LiAlH4
H+
ethanal
2.
O
CH3 C CH3
propanone
NaBH4/H+
or H2/pt
38
Purpose
Bradys
H2N
NH
O2N
NO2
Observation
To determine
carbonyl
functional
group
+ : yellow /
orange
precipitate
To determine
aliphatic
aldehyde
+ : brick-red
precipitate
2,4dinitrophenylhydrazine
Fehlings
/Benedict
Cu2+, OH -
39
Tollens
[Ag(NH3)2] +,OH
Schiffs
Iodoform
I2, OH-
To determine
aldehyde
+ : silver
mirror
To determine
aldehyde &
propanone
+ : pinkish
purple
solution
To determine + : yellow
methyl
precipitate
carbonyl &
methyl alcohol
structure,
CH3
|
-C=O
40
CH3
|
-C-OH
|
41
Structure
O
R
OH
RCOOH or RCO2H
(R alkyl, aryl or H)
NOMENCLATURE
CH3CH2CH2COOH
Butanoic acid
Butyric acid
CH3COOH
Ethanoic acid
Acetic acid
CH3CH2COOH
Propanoic acid
Propionic acid
CH3CH2CH2CH2COOH
Pentanoic acid
Valeric acid
IUPAC Nomenclature
The longest chain must contain the carboxyl group.
The carboxyl group is at the terminal, therefore the carbon
of the carboxyl group is not numbered.
One COOH carboxyl group is at one end
Two COOH carboxyl groups are at both ends
Name the compound as alkane, drop e in alkane and
add oic acid (eg: methanoic acid)
CH3
Br
CH3
CH
CH
O
CH2 C
OH
4-bromo-3-methylpentanoic acid
CH3
HO
OH
5-hydroxyhexanoic acid
O
HO
C CH2 CH
CH3
CH
CH
CH3
5-methyl-3-hexenoic acid
6
HO
OH
pentanedioic acid
HO
CH3
C CH2
CH CH2 CH2 C
OH
3-methylhexanedioic acid
CH2 COOH
C
HOOC CH2
C
H
Cl
COOH
4-chlorobenzoic acid
HOOC
COOH
1,3-benzenedicarboxylic acid
HOOC
CH3
CH CH3
COOH
2-isopropyl-1,4-benzenedicarboxylic acid
10
COOH
cyclopentanecarboxylic acid
11
COOH
cyclohexanecarboxylic acid
CH3
Br
COOH
4-bromo-2-methylcyclohexanecarboxylic acid
12
COOH
1,2-cyclohexanedicarboxylic acid
COOH
COOH
Cl
4-chloro-1,2-cyclohexanedicarboxylic acid
13
CH3
3-methyl-2-cyclohexenecarboxylic acid
14
PHYSICAL PROPERTIES OF
CARBOXYLIC ACIDS
15
Boiling Point
The boiling point of carboxylic acid is higher than an
alcohol, a ketone or an aldehyde (with Mr that almost the
same) because:
i. it exists as stable dimers that form hydrogen
bond.
ii. molecules in dimers are arranged closely
packed, therefore the hydrogen bonds are
relatively strong.
iii. high energy is needed to overcome the
intermolecular forces ,
boiling point
16
Hydrogen bond
O
R
O
C
C
O
O
Hydrogen bond
17
Solubility
a) Solubility in water
Carboxylic acids are soluble in water due to the
formation of hydrogen bond between the water
molecules and carboxylic acid molecules.
Hydrogen Bonds
O
R
H
O
C
O
C
H
O
18
O
hydrophilic
hydrophobic
C OH
19
20
COOH
CH3 CH
COOH
CH2 CH2
COOH
>
CH3 CH2 CH2
>
COOH
COOH
>
CH3 CH2 CH2 CH2
21
b.
O
C
C
O
23
Resonance Effect
O
Carboxylate ion
O-
OPhenoxide ion
24
OH
O
R
OH
>
>
H2O
>
OH
26
+ H2O
+ H3O+
O
O
carboxylate ion
(resonance structure)
OH
carboxylic acid
OH
+ H2O
ROH + H2O
+
H3O+
phenoxide ion
(resonance structure)
phenol
alcohol
RO
alkoxide ion
H3O+
27
Inductive Effect
O
EWG
EDG
O
An electron withdrawing
group (deactivating group)
that attached to a
carboxylate ion will
delocalise the negative
charge, thereby stabilises
the carboxylate ion and
increases acidity.
An electron donating
group, (activating group)
will destabilise the
carboxylate ion and
decreases acidity.
28
i.
electron-withdrawing groups
(e.g NO2 ,-F,-Cl,-Br, -I ) reduce the electron
density of
O H.
Thus the O-H bond becomes weaker and H+
can be easily released.
The compound is said to be more acidic
Electron- withdrawing group increases the
acidity.
29
Example:
CH3CHCl-COOH and CH3CH2COOH
Cl is an electron-withdrawing groups, therefore reduce
the electron density of OH.
Thus the O-H bond becomes weaker and H+ can be
easily released.
Acidity :
CH3CHCl-COOH > CH3CH2COOH
Electron-withdrawing groups increase the acidity.
30
32
Example:
CH3COOH and CH3CH2COOH
SYNTHESIS OF
CARBOXYLIC ACIDS
35
C
H
1o alcohol
R
OH
oxidizing
agent
R
C
oxidizing
agent
H
aldehyde
HO
carboxylic acid
oxidizing
agent
Cl
COOH
Cl
CH3
CH
CH3
KMnO4 , H+
COOH
+ CO2 + H2O
37
NaCN
CH2 Br
R CH2 CN
H2O,H+
CH2 CN
NaCN
R CH2 COOH
CH2 COOH
H2O,H+
38
RMgX
C
O
H2O, H+
CH2 MgBr
RCOOH + Mg(OH)X
CH2 COOH
CO2
H2O, H+
+ Mg(OH)Br
39
CHEMICAL PROPERTIES OF
CARBOXYLIC ACIDS
40
41
O
+ NaOH
OH
+ H2O
-
O Na+
42
COO Na+
COOH
+ NaOH
+ H2O
Sodium benzoate
43
O
R
C OH
C O M
H2
Exercise:
Cl
O
C
OH
44
b.
O
R
C OH
C Cl + SO2 + HCl
O
PCl5
C Cl + POCl3 + HCl
O
PCl3
C Cl + H3PO3
45
Exercise :
SOCl2
O
CH3 CH C OH
PCl5
CH3
PCl3
46
2. Esterification
Carboxylic acids react with alcohols in the presence of mineral
acid catalyst to produce esters.
O
R
O
OH + HOR
carboxylic acid
H+
alcohol
O R' + H2O
ester
O
CH3 CH2 C OH + HOCH2CH3
propanoic acid
ethanol
H+
+ H2O
47
C OH + HO C
heat
R C
C R + H2O
acid anhydride
CH3 C
OH + CH3 C
O
OH
heat
CH3 C
O
O
C CH3
ethanoic anhydride
+ H2O
48
4. Amides formation
Reaction of carboxylic acids with an
ammonia or amine give amide.
O
NH3
R C NH2 + H2O
1o amide
O
R
C Cl
RNH2
(1o amine)
NHR + H2O
2o amide
O
R2NH
(2o
amine)
NR2 + H2O
(3o amide)
49
Exercise :
NH3
CH3
CH C
Cl
CH3 NH2
CH3
CH3 NH
CH3
50
R'
LiAlH4
ether
R CH2 OH + ROH
1o alcohol
O
CH3 CH C O CH2 CH3
CH3
LiAlH4
ether
CH3 CH CH2 OH
CH3
+ HOCH2CH3
51
O
H C
carbonyl
KMnO4 / H+
(Brown)
H C OH
Ag(NH3)2+
Ag + CO2 + H2O
53
DERIVATIVES OF
CARBOXYLIC ACIDS
54
R C Cl
H2O
acid chloride
R C OH + HCl
carboxylic acid
R C O C R
acid
anhydride
O
H2O
2 R C OH
carboxylic acid
55
H2O
H+
+ ROH
carboxylic acid
R C OR
ester
alcohol
O
H2O
+
NaOH R C O Na
+ ROH
alcohol
56
Example :
O
C Cl
H2O
benzoyl chloride
CH3 C O C CH3
H2O
ethanoic anhydride
57
Example :
O
CH3 C O CH3
H2O
H+
methyl ethanoate
58
59
R C Cl , R C O C R , R C OR , R
acid
chloride
acid
anhydride
ester
< NH2
O
C
O
OH , R
carboxylic
acid
NH2
amide
reactivity increases
60
ACYL CHLORIDE
61
ANHYDRIDE ACID
Anhydride acid is more reactive than ester and
amide because the carboxyl group of anhydride is
attached to the carbonyl carbon.
O
R
O
O
R'
62
ESTER
Ester is less reactive towards nucleophile because the
delocalization of electron makes the positive charge of
carbon can be shifted to oxygen.
That makes the carbonyl carbon less electropositive.
H3C
H3C
C
R
O
R
H3C
C
R
63
AMIDE
Amide is the least reactive because, NH2 group is an
electron-donating group that makes the carbonyl less
electropositive.
The resonance structure of amide shows that the
carbonyl carbon is not electropositive.
N
-
H
64
Uses
Polyamide (Nylon)
carpet, apparel
Ester
Artificial flavors
Acetic acid
Vinegar
Ethanoic anhydride
Drug aspirin
Salicylic acid
analgesic
65
19.1
Introduction
Amines are organic derivatives of
ammonia, NH3
Classification of Amines
Primary amines
Secondary amines
R'
Tertiary amines
R''
N
R
R'
19.1
ii. CH3CH2
Aliphatic amines
CH3
iii. CH3CH2
CH3
CH3
iv.
CH3
H
v.
NH2
vi.
CH3
3
CH2CH3
Aromatic amines
19.2
IUPAC Nomenclature
In primary amines, the suffix amine
replaces the e in the name of the parent
alkane
i. CH3CH2CH2NH2
3 2
1
propanee
amine
2
N
CH3
N-methylethaneamine
19.2
Examples:
Structure
CH3NH2
CH 3 CH(NH 2 )CH 3
NH2
CH 3CH 2CHCH2CH3
IUPAC Name
Methanamine
2-propanamine
Cyclopentanamine
N-methylpentanamine
NHCH3
CH3
CH3CH2
CH2CH3
N-ethyl-N-methyl
ethanamine
19.2
IUPAC Nomenclature
When multiple functional groups are
present and the NH2 group does not
take priority, it is named as an amino
substituent
Examples:
NH2CH2COOH
2
H 2N
1
3
2-aminoethanoic acid
OH
NH2
2,4-diaminophenol
19.2
IUPAC Nomenclature
Aromatic amines are named as
derivatives of aniline
N-ethyl-N-methylaniline
19.2
Common Name
Most primary amines are named as
alkylamines
Structure
CH3NH2
IUPAC Name
methylamine
CH 3CH 2NH 2
ethylamine
CH3CH2CH2NH2
propylamine
CH 3 NHCH 3
CH3NHCH2CH3
dimethylamine
methylethylamine
19.3
Boiling point
Solubility
Basicity
HCH3
CH3
H CH3 NN CH
3
H
hydrogen bonds
CH3
CH3
CH3N NCH H
CH3
N
CH3
no hydrogen bond
hydrogen bonds
CH3
Examples:
The table below compares the boiling points of isomeric
amines.
Amines
Class
Relative
molecular
mass
Boliling
points/oC
CH3CH2CH2NH2
59
49
CH3CH2-NH-CH3
CH3
|
CH3-N-CH3
2
3
59
59
37
4
19.3
Boiling point
Solubility
Basicity
Type
Relative
molecular mass
Boliling
points/oC
CH3CH2CH2CH3
butane
CH3CH2Cl
chloroethane
CH3CH2CH2NH2
1-propanamine
Alkane
58
-0.5
Haloalkane
64.5
12.5
Amine
59
48.6
19.3
Boiling point
Solubility
Basicity
Type
Relative
molecular mass
Boiling
points/oC
CH3CH2CH2CH3
butane
CH3CH2Cl
chloroethane
CH33CH
CH22CH22NH
CH
NH22
1-propanamine
CH3CH2CH2OH
1-propanol
Alkane
58
-0.5
Haloalkane
64.5
12.5
Amine
59
48.6
Alcohol
60
97.2
Carboxylic
acid
60
118
CH3COOH
ethanoic acid
19.3
Boiling point
Solubility
Basicity
(ii) Solubility
All amines including tertiary amines,
are capable of forming hydrogen
bonds with water molecules. Thus
simple amines (amines of fewer than
5 carbons) are generally water
soluble and dissolve to form basic
aqueous solutions
R N
R : N3H< 2 < 1R N R
TheHsolubility
H
R
R
Increasing2osolubility
1
O
3o
H
R
H
O
N
R
3 hydrogen bonds
per a 1 amine
molecule
: hydrogen bonds
2 hydrogen bonds
per a 2 amine
molecule
1 hydrogen bond
per a 3 amine
molecule
19.3
Boiling point
Solubility
Basicity
An amine is a nucleophile (a Lewis base)
base
because its lone pair of non-bonding
electrons on nitrogen
Basicity
+ H OH
H
Ammonia
H + OH
H
Ammonium ion
19.3
Boiling point
Solubility
Basicity
+ H OH
1 Amine
Stabilised by the
alkyl group
H + OH
alkylammonium ion
Stronger base
Boiling point
19.3
R
+ H OH
1 Amine
Basicity
R
R
N
H
H + OH
H
alkylammonium ion
Solubility
+ H OH
2 Amine
OH
H
alkylammonium ion
Increasing
19.3
Boiling point
Solubility
Basicity
NH2
Cyclohexylamine
pKb = 3.36
NH2
Aniline
pKb = 9.42
19.3
Boiling point
Solubility
Basicity
NH2
NH2
NH2
19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides
Zn/H+ or
NO2
nitrobenzene
SnCl2/H+
NH2
Aniline
anline
19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides
Reduction of nitriles
Nitriles are reduced to primary amines
by H2 / catalyst, LiAlH4 / H+ or
NaBH4 / H+.
H2
R C N
RCH2NH2
Example :
OH
CN
1. LiAlH 4
2. H
OH
CH 2 NH 2
19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides
Reduction of amides
Reduction of an amide using LiAlH4 / H+
or NaBH4 / H+ can yield a primary,
secondary, or tertiary amine
depending on the type of amide used
O
1. LiAlH 4
R C NH 2 2. H +
H
R C NH 2
H
H 2O
19.4
Reduction of
nitro compound
Example :
O
i.
CH3
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides
C NH 2
H
1. LiAlH 4
2. H
CH3
Ethanamide
(2o amide)
ii.
Ethanamine
(1o amine)
O CH3 1. NaBH4
CH3
C NH
N-methylethanamide
(2o amide)
C NH 2 + H2O
2. H
CH3
H CH
3
C NH + H2O
H
N-methylethanamine
(2o amine)
19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides
Br2 , NaOH
H2O
RNH2
2CO3
amine
19.4
Reduction of
nitro compound
Reduction of
nitriles
Reduction of
amides
Hoffmanns
degradation of
amides
Example :
CONH2
NH2
Br2, OH-
+
H2O
CO32-
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
H
2 R N H
Cl C CH 3
2 R N H + Cl C CH3
2o amine
R N C CH3
RNH3 Cl -
2o amide
1o amine
H O
R O
R N C CH3
R2NH+2 Cl
3o amide
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
1o amine
H O
R N H + CH3 C O C CH 3
R N
R
2o amine
CH3COO H
R O
CH 3 C O C CH 3
R N C CH3
acid anhydride
3o amide
+
Formation of dye
C CH 3
2o amide
acid anhydride
+
R N H
Bromine water
CH3COO H
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
19.5
Reaction with :
Acyl chloride
1 amines
Benzenesulphonyl chloride reacts with a
1 amine to form a white precipitate
(N-substituted sulphonamides)Acidic hydrogen
Acid anhydride
Benzenesulphonyl
chloride
R-N-H
Nitrous acid
Bromine water
Formation of dye
1o amine
O
+
Cl-S-
OH
H O
R-N -S-
(-HCl)
Na O
R-N -S-
O
N-substituted
benzenesulphonamides
(precipitate)
19.5
Reaction with :
Acyl chloride
2 amines
Benzenesulphonyl chloride reacts with a
2 amines to form a white precipitate
(N,N-disubstituted sulphonamide)
Acid anhydride
R'
Benzenesulphonyl
chloride
R-N-H
Nitrous acid
Bromine water
Formation of dye
2 amine
O
+
Cl-S-
OH
(-HCl)
O
R' O
R-N -SO
N,N-disubstituted
benzenesulphonamides
(precipitate)
19.5
Reaction with :
3 amines
3 amine do not gives visible reaction
with benzenesulphonyl chloride
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
clear
NaOH
do not
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
19.5
1 amines (Aliphatic)
Primary aliphatic amines react with
nitrous acid to yield highly unstable
aliphatic diazonium salts
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
R-N-H
NaNO2, HX
o
-5 to 0 C
1 amine
Nitrous acid
[ R-N
NX ]
-N2
aliphatic
diazonium salt
(unstable)
Bromine water
Observation :
Formation of dye
C=C
carbocation
ROH
RX
19.5
Reaction with :
1 amines (Aromatic)
Primary arylamines react with nitrous
acid to give arenediazonium salts
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
N2+Cl
NH2
NaNO2, HCl
cold
+ NaCl + H2O
arenediazonium salt
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Identification
test
Aniline reacts with aqueous bromine to
yield white precipitates
NH2 group is an activating and orthopara directors group
NH2
NH2
3Br2(aq)
Br
Br
room temperature
Bromine water
Br
Formation of dye
(2,4,6-tribromoaniline)
Observation: White precipitate formed
3HBr
19.5
Reaction with :
Acyl chloride
Acid anhydride
Benzenesulphonyl
chloride
Nitrous acid
Bromine water
Formation of dye
Formation of dye
Primary arylamines react with nitrous acid
to give arenediazonium salts which are
stable at 0 C
Arenediazonium salts also undergo coupling
reaction with aromatic compounds with
strong electron donating group, such as OH
and NR2 at the para position to yield azo
compounds
Azo compounds are usually intensely
coloured and relatively inexpensive
compounds, they are used as dyes
19.5
Reaction with :
OH
Acyl chloride
N=N
Acid anhydride
OH
(orange)
+
Benzenesulphonyl
chloride
N N: X
Nitrous acid
Bromine water
Formation of dye
CH3
CH3
CH3
N=N
(yellow)
CH3
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Amino acid:
acid a compound that contains
both an amino group, -NH2 and a
carboxyl group, -COOH
H
20 amino acids
Naming
CH 3 CH 2
Zwitterion
Isoelectric point
Structures in:
NH 2
Acidic
Basic
pI
COOH
NH 2
COOH
CH 2 CH 3
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Name
Glycine
Gly
Alanine
Ala
Valine
Val
Structure
H
CH
COOH
NH2
H3C
CH
COOH
NH2
CH 3
HC
CH
CH 3 NH 2
COOH
Name
Leucine
Leu
Structure
C H
C H C H
C H
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Isoleucine
Ile
Phenylalanine
Phe
3
2
C H
N H
CH 3CH 2CH
C O O H
2
CH
CH 3
COOH
NH2
CH2
CH COOH
NH2
Zwitterion
Isoelectric point
Name
Threonine
Thr
Cysteine
Cys
Structures in:
Acidic
Basic
pI
Methionine
Met
Structure
OH
CH
CH 2
CH
NH
COOH
2
CH 2
COOH
C
CH 2
HO
NH
CH2 CH
NH2
COOH
Zwitterion
Isoelectric point
Name
Basic
pI
Structure
O
Tryptophan
Trp
Proline
Pro
Structures in:
Acidic
Serine
Ser
OH
NH2
NH
CH 2
CH 2
COOH
C
CH 2
HO
NH
CH2 CH
NH2
COOH
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Name
Structure
OH
Threonine
CH3 C
Thr
H
Cysteine
Cys
HS
CH2
CH
NH
COOH
2
CH
COOH
NH2
Methionine CH S CH CH CH COOH
3
2
2
Met
NH2
Zwitterion
Isoelectric point
Name
Structure
Tyrosine
Tyr
HO
Asparagine
Asn
Structures in:
Acidic
Basic
pI
Glutamine
Gln
CH2
CH
COOH
NH2
NH2CCH2CH COOH
O
NH2
NH2CCH2CH2CHCOOH
O
NH2
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Name
Structure
Aspartic
HOOCCH2CHCOOH
acid
NH2
Asp
Glutamic HOOCCH2CH2CHCOOH
acid
NH2
Glu
Lysine
H2NCH2CH2CH2CH2CH COOH
Lys
NH2
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Name
Structure
H2NCNH(CH2)3CHCOOH
Arginine
NH
NH2
Arg
Histidine
His
HCC=CH2CH COOH
N NH
NH2
CH
IUPAC Name
i)
H
20 amino acids
pI
NH2
Structures in:
Basic
CH3
ii)
Isoelectric point
Acidic
NH2
Naming
Zwitterion
CH2OH
iii)
NH2
COOH
2-amino-3-hydroxy
propanoic acid
IUPAC Name
CH2CH2CH2NH2
iv)
20 amino acids
COOH
Naming
NH2
Zwitterion
Isoelectric point
v)
CH2CH2CH2COOH
Structures in:
H
Acidic
Basic
pI
NH2
COOH
Zwitterion
Amino acids can undergo an
internal acid-base reaction, in which a
proton is transferred from the
carboxyl (-COOH) to the amino group
(-NH2) to form dipolar ion called
zwitterion.
-amino acid
20 amino acids
Naming
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
CH2CH2CH3
H
COOH
NH2
(neutral)
CH2CH2CH3
H
COO
NH3
(dipolar ion @
zwitterion)
20.1
-amino acid
20 amino acids
Naming
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
(Lys)
Amino Acid
NH2
Structure
Aspartic
Glycine
acid
(Gly)
(Asp)
HOOCCH
CHCOOH
H
CH 2 COOH
N H 2 NH2
pI
2.9
6.1
In Acidic
The cation, H3N+ CH2 COOH
predominates (Amino acids as base)
c
In Basi
The anion, H2N CH2 COOpredominates (Amino acids as acid)
I n pI
The zwitterion, H3N+CH2COOpredominates (Amino acids as
amphoteric)
20.1
-amino acid
20 amino acids
Naming
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
NH2CH2COOH
at pH < 6.1
at pH = 6.1
at pH > 6.1
HCl
R'
_
+
R C NH3Cl
COOH
COOH
Example:
CH2CH3
H C NH2
COOH
CH2CH3
+
HCl
H C NH3Cl
COOH
R'
R C NH2
COOH
NaNO2 / HCl
o
-5 to 0 C
HNO2
Reactions of
-COOH group:
R C
COOH
diazonium ion
elimination of N2(g)
Observation: Bubbling
of gas (N2)
R'
R C+
COOH
carbocation
NaOH
ROH
H 2O
Peptide bond
2-hydroxy
Importance
carboxylic acid
+ Cl
halocarboxylic
acid
-H
+
Alkenoic
acid
CH3
H C NH2
NaNO2 / HCl
COOH
CH3
H C
COOH
diazonium ion
elimination of N2(g)
CH3
H C+
COOH
carbocation
H 2O
CH3
H C OH
COOH
+ Cl
-H
CH3
H C
Cl
COOH
CH2
H C
COOH
NaOH
R'
R C NH2
_
COO Na+
COOH
Example:
CH2CH3
CH2CH3
H C NH2
COOH
NaOH
H C NH2
_
COO Na+
R''OH
COOH
R'
R C NH2
+ H 2O
COOR''
Example:
CH2CH3
H C NH2
COOH
HCl
CH3OH
R'
R C NH2
COOR''
+ H 2O
Peptide Bond
2 amino acids react together, H2O
is eliminated.
This is condensation reaction.
Peptides are amino acid polymers
in which the individual amino acid
units, are linked together by amide
bonds, or peptide bonds
2 amino acids form dipeptide
3 amino acids form tripeptide
15 30 amino acids form oligopeptide
> 30 amino acids form polypeptide
H
H2N CH2 C OH + H N C COOH
H CH3
O
Notes:
H2N CH2 C
N C COOH + H O
N-terminal (with free NH2) 2is
H CH3
H
H N C COOH
H
Gly
CH2
OH
H N C COOH
CH3
H
Tyr
Ala
H O
H2N CH2 C N C C
H CH3
CH2
N C COOH
H
A tripeptide
OH
Importance of proteins :
Proteins are the most abundant organic
molecules in animals, playing important
roles in all aspects of cell structure and
function.
Examples of protein functions :
Class of protein
structural protein
Examples
collagen, keratin
Importance
tendons, skin
hair, nails
ROH
Peptide bond
Functions
enzymes
DNA polymerase
repair DNA
transport protein
hemoglobin
transport O2
CHAPTER 21
POLYMERS
FJ/Chemistry Unit, KMPk/Mac 2006
21.1 : Introduction
-
Polymer
is a macro molecule that is made up of many small
repeating units called monomers linked together by
covalent bond.
nA
-A-A-A-A-A-A-A-A-n
monomer
-
polymer
nA
-A-n
polymer
(repeating unit)
Monomer
is a basic molecular units that can joined to many others
to form a polymer.
Homopolymer
-
nA
-A-n
Example :
nCH2 CH2
ethene
(ethylene)
-CH2CH2-n
polyethene
(polyethylene)
Copolymer
-
nA + nB
-A-B-n
Example :
-CH2-CCl2-CH2-CHCl-n
Saran
-A-A-A-A-A-A-A-A-n
monomers link together
in a straight chain
folded linear polymer
in a random fashion
-A-A-A-A-A-A-A-A-A-A-A-AX
CH3
CH3
-CH2C CH-CH2-
-CH2C CH-CH2-
sulphur
CH3
CH3
CH3
Proteins
Protein are the most abundant organic molecules in animals
such as enzymes, hormones, hemoglobin and many other
things.
It is a natural polymer built from amino acids linked by
amide bonds.
H O
HN-C-C
R
ii. Carbohydrates
Carbohydrates such as starch is also a polymer.
i.
Starch (amylose)
H
O
CH2OH
O
HH
H
OH H
O
CH2OH
O
H
H
OH H
O
OH
OH
-(1,4)-glycosidic linkages
contains
linkages.
-(1,4)-glycosidic
and
-(1,6)-glycosidic
n CH2=C-CH=CH2
-CH2-C=CHCH2-
CH3
CH3
isoprene
cis-polyisoprene
bond
in
natural
rubber
are
cis-
10
11
Therefore,
addition
polymer
always
involves
the
polymerization of monomers which have double bond within
the monomers.
Peroxide is used as initiator in addition polymerization.
i.
Formation of polyethene
n CH2 CH2
ROOR
ethene
-CH
( 2-CH2)n
polyethene
n HC CH2
Cl
chloroethene
ROOR
(
-HC-CH
)n
2Cl
polychloroethene
(polyvinyl chloride or PVC)
12
n HC CH2
ROOR
phenylethene
(styrene)
(
-HC-CH
)n
2-
Polyphenylethene
(polystyrene)
n CH 2 =C-CH=CH 2
-CH 2 -C=CHCH 2-
CH 3
CH 3
isoprene
polyisoprene
13
14
(A). Polyamides
i.
n H2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH
hexane-1,6-diamine
hexane-1,6-dioic acid
O
H
H O
(
-N-(CH
)n + n H2O
2)6-N-C-(CH2)4-CNylon 6,6
ii. Formation of Nylon 6
O
n H2N-(CH2)5-C-OH
6-aminohexanoic acid
O
(
-NH-(CH
)n + n H2O
2)5-CNylon 6
15
H
n H-N-
-N-H + n Cl-C-
1,4-diaminobenzene
H
N-
O
-C-Cl
terephthalic acid
H O
-N-C-
-C n
+ n HCl
Kevlar
(B). Polyester
The repeating functional groups in this polymer chain are
ester.
The most familiar polyester is polyethylene terephthalate
known as Dacron and Terylene.
16
Formation of Dacron
O
n CH3O-C-
O
-C-OCH3 + n HO-CH2CH2-OH
1,2-ethanediol
(ethylene glycol)
dimethyl terephthalate
O
(
-O-CH
2CH2-O-C-
O
-C)n + n CH3OH
metanol
17
O
n HO-CH 2CH 2-OH
+ n HO-C-
ethane-1,2-diol
O
-C-OH
benzene-1,4-dicarboxylic acid
O
(
-O-CH
2CH 2-O-CTerylene
O
-C)n + n H 2O
water
18
Polymer
Uses
Polyethene
Polyvinyl chloride
Polystyrene
Nylon 6
Textile
Nylon 6,6
Sweater
Kevlar
Dacron
Fabric
Terylene
Fiber-optic material
19