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Chemistry Malaysian Matriculation Full Notes Amp Slides For Semester 1 and 2 PDF
Chemistry Malaysian Matriculation Full Notes Amp Slides For Semester 1 and 2 PDF
Chemistry Malaysian Matriculation Full Notes Amp Slides For Semester 1 and 2 PDF
CHEMISTRY
CHEMISTRY
CHEMISTRY
CHEMISTRY SK016
Chapter Topics Hours
1.0 Matter 7
2.0 Atomic Structure 7
3.0 Periodic Table 4
4.0 Chemical Bonding 2
5.0 State of Matter 7
6.0 Chemical Equilibrium 5
7.0 Ionic Equilibria 12
Total 54
08/16/11 matter 2
CHEMISTRY SK026
Chapter Topic Hours
8.0 Thermochemistry 4
9.0 Electrochemistry 6
10.0 Reaction Kinetics 7
11.0 Intro To Organic Chemistry 4
12.0 Hydrocarbons 8
13.0 Aromatic Compounds 3
14.0 Haloalkanes (Alkyl halides) 4
15.0 Hydroxy compounds 3
08/16/11 matter 3
CHEMISTRY SK026
Chapter Topic Hour
16.0 Carbonyl 4
17.0 Carboxylic acids & Derivatives 4
18.0 Amines 5
19.0 Amino acids and Proteins 2
20.0 Polymers 1
08/16/11 matter 4
ASSESSMENT
1. COURSEWORK (20%)
Continuous evaluation (tutorial/test/quiz) - 10%
Practical work - 10%
08/16/11 matter 6
GENERAL CHEMISTRY – Principle and Modern
Applications, 8th Ed. Ralph H. Petrucci, William
S. Harwood, Prentice-Hall
08/16/11 matter 7
Chapter 1 : MATTER
1.1 Atoms and Molecules
1.2 Mole Concept
1.3 Stoichiometry
08/16/11 matter 8
1.1 Atoms and Molecules
08/16/11 matter 9
Learning Outcome
At the end of this topic, students should be
able to:
08/16/11 matter 10
Introduction
Matter
Anything that occupies space and has
mass.
e.g: air, water, animals, trees, atoms, etc
08/16/11 matter 11
Classifying Matter
08/16/11 matter 12
A substance is a form of matter that has
a definite or constant composition and
distinct properties.
Example: H2O, NH3, O2
08/16/11 matter 13
An element is a substance that cannot be
separated into simpler substances by
chemical means.
Example : Na, K, Al,Fe
08/16/11 matter 15
1.1 Atoms and Molecules
a) Atoms
An atom is the smallest unit of a chemical
element/compound.
In an atom, there are 3 subatomic particles:
- Proton (p)
- Neutron (n)
- Electron (e)
08/16/11 matter 16
Modern Model of the Atom
08/16/11 matter 17
All neutral atoms can be identified by the
number of protons and neutrons they
contain.
08/16/11 matter 19
Isotope
Isotopes are two or more atoms of the same
element that have the same proton number in
their nucleus but different nucleon number.
08/16/11 matter 20
Examples:
1 2 3
1 H H (D)
1 H (T)
1
235 238
92 U 92 U
Isotope Notation
An atom can be represented by an isotope
notation ( atomic symbol )
X= Element symbol
A= Nucleon number of X
= p+n
08/16/11 matter 22
Nucleon number of
mercury, A = 202 Total charge on
the ion
08/16/11 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:
08/16/11 matter 25
Exercise 2
Write the appropriate notation for each of the
following nuclide :
A 2 2 2
B 1 2 0
C 1 1 1
D 7 7 10
08/16/11 matter 26
b) Molecules
A molecule consists of a small number of
atoms joined together by bonds.
08/16/11 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
08/16/11 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.
08/16/11 matter 30
Mass of an atom is often expressed in atomic
mass unit, amu (or u).
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:
08/16/11 matter 32
ii) Relative Molecular Mass, Mr
A mass of one molecule of a
compound compared to 1/12 mass of one
atom of 12C with the mass 12.000amu
08/16/11 matter 33
The relative molecular mass of a
compound is the summation of the
relative atomic masses of all atoms in
a molecular formula.
Example 2
08/16/11 matter 35
MASS SPECTROMETER
An atom is very light and its mass cannot be
measured directly
A mass spectrometer is an instrument used to
measure the precise masses and relative
quantity of atoms and molecules
08/16/11 36
08/16/11 matter 37
Mass Spectrum of Monoatomic Elements
Modern mass
spectrum converts
the abundance into
percent abundance
08/16/11 38
Mass Spectrum of Magnesium
The mass spectrum of Mg
Relative abundance
08/16/11 matter 39
Learning Outcomes
08/16/11 matter 40
How to calculate the relative atomic
mass, Ar from mass spectrum?
Ar is calculated using data from the mass
spectrum.
The average of atomic masses of the entire
element’s isotope as found in a particular
environment is the relative atomic mass, Ar of
the atom.
(isotopicmass abundance
)
Averageatomicmass
abundance
08/16/11 matter 41
Example 1:
Calculate the relative atomic mass of neon
from the mass spectrum.
08/16/11 42
Solution:
= 20.2 u
08/16/11 44
Solution:
Average atomic
=
(%abundance isotopicmass)
mass of Cu % abundance
(69.09 62.93 u) (30.91 64.93 u)
= (69.09 30.91)
= 63.55 u
08/16/11 46
Solution:
= 192.254 u
_ _
+
Cl2
35Cl-35Cl+
35Cl-37Cl+
Cl2 + e Cl2+ + 2e
37Cl-37Cl+
Cl2 + e 2Cl+ + 2e
35Cl+
37Cl+
Mass Spectrum of Diatomic
Elements
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:
6.02 10N
23 atoms
3 6.02 10H
23 atoms
1 mol of CuCl2 contains 6.02 1023 Cu2+ ions
23- ions
2 6.02 10Cl
Mole and Mass
Example:
Relative atomic mass for carbon, C = 12.01
Mass of 1 C atom = 12.01 amu
Mass of 1 mol C atoms = 12.01 g
= 1.995 x 10-23 g
12.01 amu = 1.995 x 10-23 g
1.995 x 10 23 g
1 amu =
12.01 amu
= 1.66 x 10-23 g
Example:
23
1.204 x 1023 molecules of N2 1. 204 10 molecules 2 mol
6.02 10 23 molecules
18 g
or
mass = mol x molar mass
= 0.25 mol x (2 x 35.45 g mol-1)
= 18 g
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
23
7.528 x 1023 CH4 molecules 16 . 05 g 7.528 10
6.02 10 23
= 20.06 g
Molar Volume of Gases
Avogadro (1811) stated that equal volumes of gases
at the same temperature and pressure contain
equal number of molecules
Molar volume is a volume occupied by 1 mol of gas
At standard temperature and pressure (STP), the
molar volume of an ideal gas is 22.4 L mol 1
Standard Temperature and Pressure
273.15 K 1 atm 760 mmHg
0 C 101325 N m-2
101325 Pa
Standard Molar Volume
08/16/11 MATTER 67
At room conditions (1 atm, 25 C), the molar
volume of a gas = 24 L mol-1
Example 1:
Calculate the volume occupied by 1.60 mol of
Cl2 gas at STP.
Solution:
At STP,
1 mol Cl2 occupies22.4 L
= 15.7 L
08/16/11 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:
(a) Mass of 1 mol CH4 16.05
= g
1 mol of H atoms
6.02 x 1023 atoms
2 mol of H atoms
2 x 6.02 x 1023 atoms
1.2 x 1024 atoms
08/16/11 MATTER 72
Exercise
A sample of CO2 has a volume of 56 cm3 at STP.
Calculate:
08/16/11 MATTER 74
- The relationship between empirical formula
and molecular formula is :
08/16/11 MATTER 75
Example:
08/16/11 MATTER 76
Solution:
C H
Mass 85.7 14.3
85.7 14.3
Number
of moles 12.01 1.01
= 7.1357 = 14.1584
3.99
4
Answer : C6H12O4
08/16/11 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
08/16/11 MATTER 80
Concentration of Solutions
A solution is a homogeneous mixture of
two or more substances:
solvent + solute(s)
08/16/11 MATTER 81
08/16/11 MATTER 82
Concentration of a solution can be expressed
in various ways :
a) molarity
b) molality
c) mole fraction
d) percentage by mass
e) percentage by volume
08/16/11 MATTER 83
a) Molarity
32.0 g
nCaCl 2
40.08 2(35.45) g mol-1
32.0 mol
Molality of CaCl2 110.98 3
271 10 kg
08/16/11 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 200.0 g
=
(2(12.01) 5(1.01) 16.00) g mol1
nwater 150.0 g
=
1
(2(1.01) 16.00) g mol
200.0 mol
Xethanol =
45.07
200.0 mol 150.0 mol
45.07 18.02
= 0.3477
Xwater = 1 0.3477
= 0.6523
d) Percentage by Mass (%w/w)
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%
e) Percentage by Volume (%V / V)
Percentage by volume is defined as the
percentage of volume of solute in milliliter per
volume of solution in milliliter.
volume of solute
%v x 100
v volume of solution
Note:
mass of solution
Density of solution
volume of solution
08/16/11 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
35.5% 250.00 mL
Vethanol
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 ºC. 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
Vsolution =
solution
masssolution = massNaOH + masswater
= 250 g
= 1250 g
1250 g
Vsolution = 1
1.33 g mL
6.25 mol
MNaOH =
1250 3
10 L
1.33
mass water
nwater =
molar mass of water
1000 g
= 1
(2(1.01) 16.00) g mol
6.25 mol
XNaOH =
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
xA + yB zC + wD
Reactants Products
i. Fe2+ → Fe3+
ii. MnO4- + → Mn2+ +
8H+ 4H2O
i. 5Fe2+ → 5Fe3+ + 5e
ii. MnO4- + 8H+ + 5e → Mn2+ + 4H2O
___________________________________
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O
___________________________________
5. Check the equation to make sure that there
are the same number of atoms of each kind
and the same total charge on both sides.
Solution :
= 12.5 g
Learning Outcome
Solution:
3 mol H2 reacts with 1 mol N2
6 mol 1 mol
3 mol
= 2 mol N2
N2 is the excess reactant
H2 is the limiting reactant
limits the amount of products formed
= 4 mol NH3
or
1 mol N2 react with 3 mol H2
H2 is not enough
limiting reactant
H2 limits the amount of products formed
3 mol H2 produce 2 mol NH3
actual yield
% yield x 100
theoretica l yield
ATOMIC STRUCTURE
2.1 Bohr’s Atomic Model
Learning Outcomes
At the end of this topic students should be able
to:-
a) Describe the Bohr’s atomic model.
b) Explain the existence of electron energy
levels in an atom.
c) Calculate the energy
1 of electron at− 18
its level
E n= − R H 2
, R H = 2.18x10 J
(orbit) using. n
Learning Outcomes
d) Describe the formation of line spectrum of
hydrogen atom.
e) Calculate the energy change of an electron
1 1 − 18
duringE =transition.
RH 2
− 2 where RH = 2.18× 10 J
n1 n2
Orbit
Bohr’s Atomic Model
Second Postulate
The moving electron
has a specific amount
of energy; its energy
is quantised.
The energy of an electron in its level is given by:
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
Bohr’s Atomic Model
Third postulate
At ordinary conditions,
the electron is at the
ground state (lowest
level).
If energy is supplied,
electron absorbed the
energy and is promoted
from a lower energy
level to a higher ones.
(Electron is excited)
Bohr’s Atomic Model
Fourth Postulate
Electron at its excited states is unstable.
It will fall back to lower energy level and
released a specific amount of energy in the
form of light (photon).
The energy of the photon equals the energy
difference between levels.
Electron is excited from lower to higher
energy level.
A specific amount of energy is absorbed
∆E = hν = E3-E1
E= Ef − E i
Where:
1 1
Ef = − RH 2
E i= − R H 2
nf ni
1 1 1 1
∆E = −R H 2 − − R H 2 Thus, ∆E = R H 2 − 2
n
n n i n f
f i
The amount of energy released by the
electron is called a photon of energy.
A photon of energy is emitted in the form of
radiation with appropriate frequency and
wavelength.
E = hv
1 1 1 7 −1
= RH 2
− 2 where R H = 1.097× 10 m
n1 n2
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. Calculate the energy of hydrogen electron in the:
Continuous Line
Spectra 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
Formation of Continuous Spectrum
Regions of the Electromagnetic Spectrum
Line Spectrum (atomic spectrum)
A spectrum consists of discontinuous & discrete
lines with specific wavelength.
It is composed when the light from a gas
discharge tube containing a particular element
is passed through a prism.
Formation of Atomic / Line
Spectrum
The emitted light (photons) is then separated
into its components by a prism.
Each component is focused at a definite
position, according to its wavelength and forms
as an image on the photographic plate.
Energy n=3
n=2
n=1
Emission of photon
Line E
spectrum λ
Lyman Series
Formation of Line Spectrum
(Balmer Series)
n=∞
n=5
n=4
Energy n=3
n=2
n=1
Emission of photon
Line E
spectrum λ
Lyman Series Balmer Series
Energy Level in Hydrogen Atom
Example
Complete the following table
Spectrum
Series nf ni
region
b)the frequency
c)the energy
Example
Refer to last line of hydrogen spectrum in Lyman
series, Calculate:
a) Wavelength
b) Frequency
− 18 1 1
= − 2.18× 10 2
− 2
1 ∞
− 18
= 2.18× 10 J
Solution
(b) 1 H atoms need 2.18 x 1018 J
1 mol H atom
= 1.31 x 106 J
Ionisation energy
= (2.18 x 10-18) (6.02x1023 J mol-1)
= 1.312 x 106 J mol-1
= 1312 kJ mol-1
The weaknesses of Bohr’s Theory
It can only explain the hydrogen spectrum or
any spectrum of ions contain one electron.
example: He+, Li2+.Therefore, it did not account
for the emission spectrum of atom containing
more than 1 electron.
Electron are wavelike, we can’t define the
precise location of a wave because a wave
extends in space.
de Broglie’s 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.
h
=
mµ
h = Planck constant (J s)
m = particle mass (kg)
µ = velocity (m/s)
λ = wavelength of a matter wave
Heisenberg’s Uncertainty Principle
It is impossible to know simultaneously both the
momentum p (defined as mass times velocity) and the
position of a particle with certain.
Stated mathematically,
h
x p≥
4π
where ∆x = uncertainty in measuring the position
∆p = uncertainty in measuring the momentum
= ∆mv
h = Planck constant
2.2 Quantum Mechanical Model
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 three-
dimensional 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
As n increase :
n 1 2 3 4
Orbital size
Energy
increases
Angular Momentum Quantum
Number, l
Alternative name:
- Subsidiary Quantum Number
- Azimuthal Quantum Number
- Orbital Quantum Number
The value of l indicates the shape of the
atomic orbital.
If n = 3, l = 0 (s-orbital)
three subshells
= 1 (p-orbital)
(s, p, and dorbitals)
= 2 (d-orbital)
Magnetic Quantum Number, m
Describe the orientation of orbitals in space.
Possible values of m depend on the value of l.
For a given l, m can be : -l, …, 0, …, +l
Example:
If l = 0, m = 0 » 1 orientation of s orbital
If l = 1, m = -1,0,+1 » 3 orientation of p orbital
(px, py, pz)
If l = 2, m = -2,-1, 0,+1,+2 » 5 orientation of d orbital
(
dxy,dxz,dyz,dx2-y2,dz2)
Electron Spin Quantum Number, s
The value of s represent the
direction of an electron rotation
on its own axis.
either clockwise or
anticlockwise
Z Z Z
Y Y Y
X X X
1s 2s 3s
Shape of Atomic Orbitals
p orbitals
Can be represent as a pair of dumb-bell shaped
When l = 1, m = -1, 0, +1
px
py pz
Shape of Atomic Orbitals
d orbitals
All the d orbitals do not look alike.
dxz dyz
Set of Four Quantum Numbers
4 quantum number n,l,m and s enable us to
label completely an electron in any orbital of an
atom. Example:
4 quantum numbers of 2s orbital electron are
n = 2 , l = 0 , m = 0 and s = +½ and -½
Orbital
Shell n l m No. of orbitals
notation
1 1 0 1s 0 1
0 2s 0 1
2 2
1 2p -1,0,+1 3
Exercise
Predict the following quantum numbers whether
they are allowed or not
(a) (1,0,0,-½)
(b) (2,0,1,1)
(c) (0,1,1,+½)
(d) (4,1,0,-½)
2.3 Electronic Configuration
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.
Box
1s 2s 2p
Electronic Configuration
Method 2: s,p,d,f notation
Example: 8O Number of electrons
in the subshells
1s 2 2s 2 2p4
4p
n=4 3d
4s
energy
Energy
n=3 3p
3s Orbital energy levels
in a many-electron atom
n=2 2p
2s
n=1
1s
Order of orbitals (filling) in multi-electron atom
Order of orbitals (filling) in multi-electron atom
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-
The Anomalous Electronic
Configurations of Cr and Cu
Cr and Cu have electron configurations which are
inconsistent with the Aufbau principle. The
anomalous are explained on the basis that a
filled or half-filled orbital is more stable.
Expected (Aufbau
Element Observed/actual
Principle)
1s22s22p63s23p6 4s2
Cr (Z=24) 1s22s22p63s23p6 4s1 3d5
3d4
1s22s22p63s23p6 3d9 1s22s22p63s23p6 3d10
Cu (Z=29)
4s2 4s1
Orbital diagram
24Cr : 18[Ar]
3d 4s
24Cr : 18[Ar]
Actual
3d 4s
Cu : 18[Ar]
3d 4s
Cu : 18[Ar]
3d 4s
1
LEARNING OUTCOMES
3
• A vertical column of elements is called a
group and a horizontal row is known as a
period.
6
• The periods in the Periodic Table are
numbered from 1 to 7
• For example, hydrogen and helium are
in Row 1 or Period 1 because their
principal quantum number, n, of the
main electron shell is 1. (H:1s1 ;He: 1s2)
7
Blocks
• All the elements in the Periodic Table can
be classified into 4 main blocks according
to their valence electrons configuration.
8
s- block
• Group 1 and 2
• The filling of valence electrons involve the s
orbital
• Configuration of the valence electrons :
ns1 to ns2
• Eg:
Na : 1s2 2s2 2p6 3s1
11
Ca : 1s2 2s2 2p6 3s2 3p6 4s2
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.
Al : 1s 2 2s2 2p6 3s2 3p1
13
Te : 1s 2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2
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).
12
elements block period group Numbe
r of
K : 1s 2 2s2
s 4 1 velenc
1
19
15
Element Group Period Class/block
Block p
B 17 4
Block s
C 2 4
Transition element/
D block d
5 4
Inert gas / block p
E
18 4
16
3.2 Periodicity
Size volume
V = 4/3 πr3 , V r
a
• Down the group, atomic radii increases.
Across period, atomic radii decreases.
18
Two factors that influence the changes of
atomic radii in the Periodic Table are:
19
i. Effective nuclear charge (Zeff )
• Electrons around the nucleus experience
different nucleus attraction.
20
• Effective nuclear charge increase, nucleus
attraction stronger, atomic radii decrease
23
Across
period 3
Across
Period 2
24
The graph shows that :
•Atomic radius decreases when :
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 Group Group
of P 14 15
• Both Si and P are in the third period and Si is N
to the left of P.
• Atomic radius decreases as we move from Si P
left to right.
• Therefore, the radius of P is smaller than Si.
• Thus the order of increasing radius :
N<P<Si
26
3.2.2 Trends in the ionic radii
• When electrons are added to an atom, the
mutual repulsions between them increase.
27
• When electrons are removed from the
valence shell, the electron-electron
repulsions decrease but the nuclear
charge remains the same.
28
29
Isoelectronic species
E.g :
• Na+, Mg2+, Al3+and Si4+ ions are isoelectronic
(10 e) with the electron configurations as
1s2 2s2 2p6.
30
Isoelectronic species with electronic configuration
1s2 2s2 2p6 (10 electrons)
species Number of
Na+ 11
proton
Mg2+ 12
Al3+ 13
Si4+ 14
•When proton number increase, effective nuclear
charge increase.
•The attraction between nucleus and remaining
electron increase.
•Therefore, the ionic radii decrease.
•The ionic radii of Na+ > Mg2+ > Al3+ > Si4+
Isoelectronic species with electronic
1s2 2s2 2p6 3s2 3p6 (18 electrons)
species Number of
P3- 15
proton
S2- 16
Cl- 17
•When proton number increase, effective nuclear
charge increase.
•The attraction between nucleus and remaining
electron increase.
•Therefore, the ionic radii decrease.
•The ionic radii of Cl- < S2- < P3-
Exercise
Answer :
N3- > O2- > F- > Na+ > Mg2+ > Al3+> Si4+
33
34
3.2.3 Trends in the ionization
energies
• The ionization energy (IE) is the minimum
energy required to remove an electron from a
gaseous atom in its ground state.
The first ionization energy (IE ) is the
1
minimum energy required to remove the first
electron from the atom in its ground state.
E.g:
energy + X(g) → X+(g) + e- ΔH = IE1
35
i) Ionization energy across a period :
■
▲
٭
♦
37
Anomalous cases in Period 2
a) Between group 2 and 13
39
ii) Ionization energy going down the group
• Going down the group, the atomic size
increases as the energy level, n increases.
42
Example 1
• 4Be
• The ionization energies (kJmol-1) of Beryllium
are shown below.
43
• The ratio between the ionization energies are:
IE 2 1757
1.95
IE 1 899
IE 3 14850
8.45
IE 2 1757
IE 4 21005
1.41
IE 3 14850
44
• A sharp increase in ionization energy
occurs when an inner-orbital electron is
removed.
45
Example 2
• Determine
i) the electron configuration of the valence
electron.
ii) the group number in the periodic table.
46
• The sharp increase is in IE5, this means
the 5th electron occupies the inner shell.
47
Trends in the electronegativity
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
Trends in the melting or boiling point
51
Across the period
Element Na Mg Al Si P S Cl Ar
Melting 98 650 660 1410 44 120 -101 -189
point
(oC)
Boiling 890 1120 2450 2360 280 445 -34 -186
point
(oC)
52
• The variation of melting and boiling point of
elements in the 3rd period can be discussed
as:
(a) Metallic structure (Na to Al)
(b) Gigantic covalent structure (Si)
(c) Simple molecular structure (P to Ar)
53
a)Metallic structure (Na to Al)
54
b) Gigantic covalent structure (Si)
55
c) Simple molecular structure ( P to Ar)
• The non-metal that exist as molecules of P4, S8,
Cl2 and Ar (monoatom).
• The covalent bond between the atoms is very
strong but the intermolecular force (Van der
Waals), is very weak.
• The strength of Van der Waals force is
proportional to molecular size (relative molecular
weight)
– Molecular size: Ar < Cl2 < P4 < S8
– therefore
melting / boiling point : Ar < Cl < P < S 56
Melting and boiling points down the group
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.
58
Metallic character
59
• The easier to the electrons to be removed
from an atom, the more metallic the
element.
Metalloids
metal nonmetal
(semimetal)
60
Acid-base behavior of oxides of Period 3
For Period 3:
Na Mg Al Si P S Cl
61
• Na reacts with oxygen to form a basic oxide.
4Na (s) + O2 (g)→2Na2O (s)
• The oxide will produce base solution when react
with water.
Na2O (s) + H2O (l) → 2NaOH (aq)
63
Si, P, S & Cl burn in oxygen to form acidic oxide.
Si :
Si (s) + O2 (g) → SiO2 (s)
SiO2 (s) + NaOH (aq) → Na2SiO3(aq)+H2O (l)
acid base
64
P:
P4 (s) + 3O2 (g) → P4O6 (s)
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
Chemical bond is the force that
holds two atoms together in a
molecule or compound
Group 1 2 13 14 15 16 17 18
Valence 1 2 3 4 5 6 7 8
electron
Lewis dot
symbol
Elements in the same group have the
same valence electronic configurations
similar Lewis symbols.
4.1.2 Octet Rule
Octet rule states that atoms tend to form
bonds to obtain 8 electrons in the valence
shell
Atoms combine to achieve stablility
to have the same electronic
configuration as a noble gas
Atoms achieve noble gas configuration
through:
i) transferring electrons
ii) sharing electron
Bond formation involve transferring or
sharing of only valence electrons
Electronic Configuration of Cations and
Anions
Ca : 1s22s22p63s23p64s2
Ca2+ : 1s22s22p63s23p6 (isoelectronic with Ar)
Group 15, 16 and 17 elements accept
electrons to form anions with noble gas
configurations
Example:
O : 1s22s22p4
O2 : 1s22s22p6
(isoelectronic with neon)
Cl : 1s22s22p63s23p5
Cl : 1s22s22p63s23p6
(isoelectronic with Ar)
2) Pseudonoble gas configuration
+
Example 2: CaCl2
Calcium Chloride
+ + 2
Example 3: LiF
+
Lewis structure and formation of ionic compounds
1) CaCl2
+ + 2
2) MgO
+
3) CaBr2
+ +
Ionic bond is very strong, therefore ionic
compounds:
1. Have very high melting and boiling
points
2. Hard and brittle
F + F F F
Lewis structure of F2
9.4
Covalent compounds:
H + O+ H H O H
2e- 8e- 2e-
or
H O H
Double bond – two atoms share
two pairs of electrons
O C O or O C O
8e- 8e- 8e-
double bonds double bonds
Triple
+
bond – two atoms share
three pairs of electrons
N N or N N
8e- 8e-
triple bond
triple bond
4.1.3.3 Coordinate Covalent Bond
(Dative Bond)
i.Double bond
i.Triple bond
Steps in Writing Lewis Structures
1. Count total number of valence e- of atoms involved.
2. Add 1 for each negative charge. Subtract 1 for each
positive charge.
3. Draw skeletal structure of the compound. Put least
electronegative element in the center.
4. Complete an octet for all atoms except hydrogen
5. If structure contains too many electrons, form double
and triple bonds on central atom as needed.
Example
Draw the Lewis structure for each of the
following compounds:
i. HF
ii. CH4
iii. CHCl3
iv. NH3
v. H2O
Total no. of valence
electrons
H: 1e
F: 7e
Total : 8e
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 : 5e
3H : 3e
Total : 8e
4.1.5 Bond Length
Compare the bond length between single,
double and triple bond
Bond length :
The distance between nuclei of the atoms involves in the
bond
C C C C C C
1.54 Å 1.34 Å 1.20 Å
1) HCN
1) CO2
1) SCN
Three conditions:
1) Incomplete octet
2) Expanded octet
Example:
Nitric oxide, NO
Nitrogen dioxide, NO2
The use of two or more Lewis
structures to represent a particular
molecule.
Requirement:
i. VSEPR theory
ii. 5 basic shapes
iii. polarity
64
Molecular shape: Introduction
65
4.2.1 VSEPR
66
The repulsion may occur either between:
Note:
The electron pairs repulsion will determine the
orientation of atoms in space
68
4.2.2 Shape of a molecule
Basic shapes are based on the repulsion
between the bonding pairs.
2Cl :14e
Total : 16 e
.. ..
:Cl Be Cl: .. Linear
..
70
B. Molecules with 3 bonding-pairs
Example: BCl3
Repulsive forces
Lewis structure between pairs are the
B: 3e
same
3Cl : 21e
Total: 24e
120°
:
Cl
..
..
.. ..
: Cl
.. B Cl :
..
Trigonal planar
71
C. Molecules with 4 bonding pairs
Example: CH4 Equal repulsion
Lewis structure between bonding pairs
– equal angle
H
H C H 109.5°
Tetrahedral
72
D. Molecules with 5 bonding pairs
Example: PCl5
Lewis structure Shape:
90°
:
Cl
..
..
..
.. Cl :
Cl
: P ..
.. 120°
..
Cl :
..
Cl
..
..
:
Trigonal bipyramidal
73
E. Molecules with 6 bonding pairs
Example: SF6
Lewis structure
Octahedral
S : 6e
6F : 42e
90o
Total : 48e
90o
F
F
F S F
F
F
74
2 electron pairs in the valence shell
of central atom:
AB2 2 0 180°
Linear
75
3 electron pairs in the valence shell
of central atom:
Class of Number Number Shape
molecules of bonding of lone
pairs pairs
AB3 3 0
120°
76
trigonal planar
4 electron pairs in the valence shell
of central atom:
Class of Number Number Shape
molecules of bonding of lone
pairs pairs
AB4 4 0
109.5o
77
Tetrahedral
5 electron pairs in the valence shell
of central atom:
120°
78
Trigonal pyramidal
6 electron pairs in the valence shell
of central atom:
90°
90°
79
Octahedral
4.2.3 Effect of lone pairs on
molecular shape
80
Repulsion between electron
pairs decreases in the order of:
81
Electrons in a bond are held by the
attractive forces exerted by the nuclei of
the two bonded atoms therefore, they take
less space of repulsion.
82
Number of electron pair : 3
Example : SO2
83
Number of electron pair : 4
Example : NH3
84
Number of electron pair : 4
Example : H2O
85
Number of electron pair : 5
Example : SF4
86
Number of electron pair : 5
Example : ClF3
87
Number of electron pair : 5
Example : I3-
88
Number of electron pair : 6
Example : BrF5
89
Number of electron pair : 6
Example : XeF4
90
Shape of molecules which the central
atom has one or more lone pairs
Bent / V-shaped
91
Bond angle : < 120o
4 electron pairs in the valence shell
of central atom:
Trigonal pyramidal
92
Bond angle : < 109.5o
4 electron pairs in the valence shell
of central atom:
Class of Number Number Shape
molecules of bonding of lone
pairs pairs
AB2E2 2 2
Bent / V-shaped
Bond angle : < 109.5o
93
5 electron pairs in the valence shell
of central atom:
Class of Number Number Shape
molecules of bonding of lone
pairs pairs
AB4E 4 1
Distorted tetrahedral
(see-saw)
94 Bond angle : < 90o
5 electron pairs in the valence shell
of central atom:
T-shaped
95
Bond angle : < 90o
5 electron pairs in the valence shell
of central atom:
Linear
96
Bond angle : 180o
6 electron pairs in the valence shell
of central atom:
Class of Number Number Shape
molecules of bonding of lone
pairs pairs
AB5E 5 1
Square pyramidal
97 Bond angle :90o and
180o
5 electron pairs in the valence shell
of central atom:
Square planar
98
Bond angle : 90o
99
COMPARISON OF BOND ANGLE
IN CH4, NH3 AND H2O
100
a) CH4
101
b) NH3
H F
105
The consequent charge separation can be
represented by :
106
Diatomic molecules containing atoms of
different elements (e.g. : HCl, NO and CO)
have dipole moments and are called polar
molecules.
107
For polyatomic molecules, the polarity of the
bond and the molecular geometry determine
whether there is a dipole moment.
108
Example
109
(a) Carbon dioxide, CO2
110
(b) Carbon tetrachloride, CCl4
111
( c) Chloromethane, CH3Cl
113
Factors that affected the
polarity of molecules
molecular geometry
114
BOND
NON-POLAR
POLAR
NON-POLAR
MOLECULES
NON-POLAR POLAR
MOLECULES MOLECULES
116
4.3 ORBITAL OVERLAP AND
HYBRIDIZATION
117
Objectives
Change in electron
density as two hydrogen
atoms approach each
other.
120
10.3
FORMATION OF COVALENT BOND
121
a) bond
H + H H H
bond
122
ii. Overlapping of s and p orbitals
Px orbital
H + x H x
bond
123
• iii. Overlapping of p orbitals
x
+ x
x
bond
124
b) bond
• Formed when two p-orbitals of the same
orientation overlap sideways
y y y y
125
bond
y y y y
bond
126
Formation of bonds in a molecule
• Covalent bonds may form by:
a) overlapping of pure orbitals
b) overlapping of hybrid orbitals
127
Overlapping of pure orbitals
• Example :
i. O2
ii. N2
128
O2
Consider the ground state configuration:
Two unpaired electrons to be used in
bonding.
O : 1s2 2s2 2p4
y y
1s 2s 2p
129
y y
O O x
σ
130
N2
131
4.3.2 Formation Hybrid orbitals
• Overlapping of hybrid orbitals and the pure orbitals
occur when different type of atoms are involved in
the bonding.
• Hybridization of orbitals:
mixing of two or more atomic orbitals to form a new
set of hybrid orbitals
133
10.4
Hybridization of orbitals
i. sp
ii. sp2
iii. sp3
iv. sp3d
v. sp3d2
134
sp3 hybridization
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
Example : Methane, CH4
Ground state : C : 1s2 2s2 2p2 Lewis Structure
H
H C H
1s 2s 2p
H
Excitation: to have 4
unpaired electrons H
C sp3
sp3 H
H sp3
sp3 hybrid H
shape: tetrahedral
138
Fig. 10.8
sp3
1s sp3 sp3 1s
sp3
1s
139
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
1s
sp3
1s
141
Example:
3) H2O
• Lewis structure :
142
sp 2 hybridization
• one s orbital and two p orbitals are
mixed to form three sp2 hybrid
orbitals
• the geometry of the three hybrid
orbitals is trigonal planar with the
angle of 120o .
143
Fig. 10.12
s sp2
px py sp2 sp2
one
144
s orbital + two p orbitals three sp2 orbitals
• simplified drawing of sp2 orbitals:
Shown together
(large lobes only)
145
Example:
1) BF3
• Lewis structure :
• Valence orbital diagram;
F:
B ground state :
B excited :
B hybrid :
• Orbital overlap:
146
Example: BF3
Pure p orbital
sp2 sp2
F : 1s22s22p5
sp2
147
Example:
2) C2H4
• Lewis structure :
• Valence orbital diagram;
C ground state :
C excited :
C hybrid :
• Orbital overlap:
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
Types of hybrid orbitals
152
10.4
Example:
1) BeCl2
• Lewis structure :
• Valence orbital diagram;
Cl :
Be ground state :
Be excited :
Be hybrid :
• Orbital overlap:
153
Fig. 10.11
154
Example:
2) C2H2
• Lewis structure :
• Valence orbital diagram;
C ground state :
C excited :
C hybrid :
• Orbital overlap:
155
Fig. 10.19a-c
156
Example:
3) CO2
• Lewis structure :
• Valence orbital diagram;
O:
C ground state :
C excited :
C hybrid :
• Orbital overlap:
157
3
sp d hybridization
• one s orbital, three p orbitals and
one d orbital are mixed to form five
sp3d hybrid orbitals.
• the geometry of the five hybrid
orbitals is trigonal bipyramidal with
the angle of 120o and 90o
158
• simplified drawing of sp3d orbitals:
159
Example:
1) PCl5
• Lewis structure :
• Valence orbital diagram;
Cl :
P ground state :
P excited :
P hybrid :
• Orbital overlap:
160
Example:
2) ClF3
• Lewis structure :
• Valence orbital diagram;
F:
Cl ground state :
Cl excited :
Cl hybrid :
• Orbital overlap:
161
3
sp d 2 hybridization
• one s orbital, three p orbitals and
two d orbitals are mixed to form six
sp3d2 hybrid orbitals
• the geometry of the six hybrid orbitals
is octahedral with the angle of 90o
162
• Simplified drawing of sp3d2 orbitals:
163
Example:
1) SF6
• Lewis structure :
• Valence orbital diagram;
F:
S ground state :
S excited :
S hybrid :
• Orbital overlap:
164
Example:
2) ICl5
• Lewis structure :
• Valence orbital diagram;
Cl :
I ground state :
I excited :
I hybrid :
• Orbital overlap:
165
How do I predict the hybridization of the central atom?
No of Lone Pairs
+
No of Bonded Atoms Hybridization Examples
2 sp BeCl2
3 sp2 BF3
5 sp3d PCl5
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
4.4 Intermolecular forces
LEARNING OUTCOMES
At the end of the lesson, students should be able
to;
1. Describe intermolecular forces
i. van der Waals forces :
- dipole-dipole interactions or permanent
dipole
- London forces or dispersion forces
ii. Hydrogen bonding
2. Explain factors that influence the strength of van der Waals
forces
3. Explain the effects of hydrogen bonding on
i. boiling point
ii. Solubility
iii. Density of water compared to ice
1. Explain the relationship between :
i. intermolecular forces and vapour pressure
ii. Vapour pressure and boiling point
4.4 Intermolecular forces
4.4.1 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
Have effects on these physical
properties:
a) boiling point
b) melting point
c) solubility
d) density
e) electrical conductivity
173
Intermolecular Forces
Between Between
covalent covalent
molecules
molecules with H
covalently
bonded to
F, O or N
174
4.4.1.1 van der Waal Forces
Forces that act between covalent
molecules
Three types of interaction:
i. Dipole-dipole attractive
forces
- act between polar molecules
ii. London Dispersion forces
- act between non-polar
molecules 175
Dipole-dipole forces
(permanent dipole forces)
Exist in polar covalent compounds
Polar molecules have permanent dipole due
to the uneven electron distributions
Example:
- +
-
+
H Cl H Cl
176
4.4.1.2. London Dispersion Forces
177
The formation of London forces
179
Factors that influence the strength of
the van der Waals forces.
The molecular size/molecular mass
Molecules with higher molar mass have
stronger van der Waals forces as they tend to
have more electrons involved in the London
forces.
Example:
CH4 has lower boiling point than C2H6
Note:
However if two molecules have similar
molecular mass, the dipole-dipole interaction
will be more dominant.
Example: H2S has higher boiling point than
CH3CH3 180
4.4.1.3 Hydrogen intermolecular bond
H F H F
Hydrogen
intermolecular bond
181
Other examples:
NH3 liquid H2O
.. Hydrogen
N intermolecular bond
H
H H .. ..
..
..
Hydrogen O O
.. intermolecular bond H H
H H
N
H
H H ..
..
O
Covalent bond H H
.. .. Hydrogen
O intermolecular bond
H H
182
Consider ethanol, CH3OH
H
Hydrogen bond Not a hydrogen
bond
.. C
.. H
..
O H H
O H H .. H
..
..
C in
H C
H H C
H
H H H is not H
bonded to H H
either F, O
or N
183
Example: H2O
___ covalent bond
H ----- hydrogen bond
O H
H H
O H O H O
H
H
H
O H 184
185
Properties of compounds with
Hydrogen intermolecular forces
Boiling point
186
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
..
..
O
Hydrogen bond
H H
..
..
N
N H
H H H
H H
188
Problem:
HF
HI
HBr
HCl
Molecular mass
189
Answer
191
Density
193
H2O(l) is denser than H2O(s) because
the hydrogen bond in ice arrange the
H2O molecules in open hexagonal
crystal
H2O molecules in water have higher
kinetic energy and can overcome
the hydrogen bond
V-shaped water molecules slide
between each other.
194
195
196
Fig. 11.13
197
Boiling points of substance with
Hydrogen intermolecular bonds
The boiling points of these substances are
affected by:
a) the number of hydrogen bonds per
molecule
b) the strength of H intermolecular
forces which directly depends on
the polarity of the hydrogen bond
Example:
Explain the trend of boiling points given below:
The order of the increase in boiling point is:
H2O > HF > NH3 > CH4
198
Answer:
by looking at the polarity of the bond, we have
(Order of polarity: HF > H2O > NH3)
but H2O has the highest boiling point.
For H2O, the number of hydrogen bonds per molecule
affects the boiling point.
Each water molecule can form 4 hydrogen bonds with
other water molecules. More energy is required to
break the 4 Hydrogen bonds.
HF has higher boiling point than NH3 because F is
more electronegative than Nitrogen.
CH4 is the lowest - it is a non polar compound and
has weak van der Waals forces acting between
molecules.
199
Effects of intermolecular forces on
physical properties
1)Boiling point
For molecules with similar size, the order of
intermolecular strength:
Hydrogen bond > dipole-dipole forces >
London dispersion forces
Strength of intermolecular forces ↑
boiling point ↑
200
201
Why boiling point H2O > HF
and HF > NH3?
202
On the other hand, H-F has only 2 hydrogen
bonds.
Therefore the hydrogen bonds are stronger
in H2O rather than in H-F.
203
Boiling point HF > NH3
Fluorine is more electronegative than
nitrogen ,thus the hydrogen bonding in H-F
is stronger than H-N.
204
Vapour Pressure
Molecules can escape from the surface of liquid
at any temperature by evaporation
in a closed system :
vapour molecules which leaves the
surface cannot escape from the system
the molecules strike the container wall
and exert some pressure
Fig. 11.34
The pressure exerted by those molecules is
called vapour pressure (or maximum vapour
pressure)
Note:
Equilibrium vapour pressure = saturated vapour pressure
= vapour pressure
Factors that affects vapour pressure
i. Intermolecular forces
Molecules with weak intermolecular forces can easily
vapourise. More vapour molecules will be present and
exert higher pressure.
the weaker intermolecular forces the higher is
the vapour pressure.
ii. Temperature
Heating causes more molecules to have high kinetic
energies that are higher than their intermolecular
forces. More liquid molecules will form vapour.
vapour pressure increases with temperature.
Fig. 11.35
Boiling – the process
Increasing the temperature will increase in the vapour
pressure.
1. Intermolecular forces
A substance with weak intermolecular
forces can easily vapourise and the system
requires less heat to achieve atmospheric
pressure, thus it boils at a lower temperature.
2. Atmospheric pressure
When the external atmospheric pressure is
low, liquid will boil at a lower temperature.
4.5 Metallic bond
LEARNING OUTCOMES
At the end of the lesson, students should be
able to;
1. Explain the formation of metallic bond by using
electron sea model.
2. Relate metallic bond to the properties of metal:
i. malleability
ii. Ductility
iii. Electrical conductivity
iv. Thermal conductivity
3. Explain the factors that affect the strength of metallic
bond
4. Relate the strength of metallic bond to boiling point
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
e e e
electrons e
e e e e
Free
moving
electrons
e e e e
218
Electrostatic force in a metal
Metallic Bond (Electron-sea Model)
Metals form giant metallic structure
Each positive ion is attracted to the
‘sea of electrons’.
These atoms are closely held by the
strong electrostatic forces acting
between the positive ions and the ‘sea
of electrons’.
These free moving electrons are
responsible for the high melting point
of metals and the electrical
conductivity. 219
Physical properties of metals
220
The strength of the metallic bonds
The strength of the metallic bond
increases with the number of valence
electrons and the size of ions.
221
Boiling points in metals
Na Mg
ee ee ee ee ee ee ee ee
+1 +1 +1 +1 +1 +1 +2 +2 +2 +2 +2 +2 +2 +2
e e e e e e ee ee ee ee ee ee ee ee
+1 +1 +1 +1 +1 +1 +2 +2 +2 +2 +2 +2 +2 +2
e e e e e e ee ee ee ee ee ee ee ee
ee
+1 +1 +1 +1 +1 +1 +2 +2 +2 +2 +2 +2 +2 +2
223
Answer
The cationic size of Al is smaller
compared to magnesium and its
charge is higher (+3).
Mg has two valence electrons
Al has three valence electrons
involved in the metallic bonding.
The strength of metallic bond in
Aluminium is greater than that of
Magnesium
Al has higher boiling point
224
The strength of metallic bond is
directly proportional to the boiling
point.
The stronger metallic bond,the
higher the boiling point.
225
CHAPTER 5.0
STATES OF MATTER
5.1 Gas
5.2 Liquid
5.3 Solid
At the end of the lesson, student should be able to :
1
V P (no of mole and temperature are constant)
PV = k Where:
k = constant
V = volume
P = pressure
T = temperature
n = number of moles
at different pressure and volume :
P1 V1 = P2 V2
Where
P1 = initial pressure
V1 = initial volume
P2 = final pressure
V2 = final volume
Graph of P versus V Graph of P versus 1
V
P
P
1
V V
pressure is inversely pressure is directly
proportional to volume proportional to 1
volume
Graph of PV versus P
PV
PV = constant
P
Example 1
0.4 atm
Example 2
46.36 mL
a) Charles’s Law :
The volume of a fixed amount of gas at
constant pressure is directly proportional to the
absolute temperature of the gas (in Kelvin).
T = absolute temperature
in Kelvin (K)
V1 V2
T1 T2 T(K) = T°C + 273.15
V V
0 T(K) -273.15
T(0C)
Example 1
-81.54 °C
Example 2
5.08 mL
The Combination of Boyle’s and Charles’s Law
1
Boyle’s law : V
P
Charles’s law : VT
T
V
P
T
V= k
P
PV
=k
T
P1V1 =
P2V2
T1 T2
Example 1
Ans : 35.32 L
Example 2
nT
V Where :
P
R = gas constant
V=R
nT
T = Temperature(K)
P
n = number of moles
PV = nRT V = volume
Ideal gas equation P = Pressure
Value of R depend on the unit of pressure and
volume used in the equation.
unit of unit of value of unit of R
pressure volume R
atm L or dm3 0.08206 L atm mol1 K1
m m
PV= RT where: n =
Mr Mr
mRT Mr = molar mass of a gas
Mr =
PV
Density of a gas
PV nRT
m
PV= RT
Mr
mRT
P=
VM r
dRT where,
P=
Mr d = density of a
gas
PM r
d=
RT
Example
1
Calculate the density of ammonia (NH3) in grams
per litre (g/L) at 752 mmHg and 55 C.
Ans : 8.0 g
Dalton’s Law of Partial Pressure
The total pressure of mixture of non reacting gases is the
sum of the partial pressures exerted by each of the gas in
the mixture
(Partial pressure is the pressure of individual gas component in a
mixture).
PT = PA + PB + PC
According to ideal gas equation :
nA RT
pressure exerted by gas A = PA =
V
nBRT
pressure exerted by gas B = PB =
V
in the mixture of gases A and B :
PT = PA + PB
n A RT nBRT
=
V V
= (nA + nB )RT n TRT
V PT =
V
when nA + nB = nT
Mole fraction and pressures
Daltons theory allows us to form a relationship
between Mole fractions, partial pressure and a total
pressure.
Consider the following condition at constant T
and V
If P n RT
A A
Ptotal ntotal(RT )
Thus: PA n A ( RT ) PA nA
Ptotal ntotal ( RT ) PTotal nTotal
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
9
Van der Waal’s Equation
Since real gas does not exhibit ideal gas behavior
at high pressure and low temperature :
the ideal gas equation (PV=nRT) needs to be
adjusted
adjusting the equation, two parameters need to
be reconsidered :
√ attractive forces between the gas molecules
√ volume of the gas molecules
a) Attractive Forces Between Molecules
Attractive forces which act between the gas molecules will :
make the molecules move slower
give less impact to the wall
pressure exerted by the real gas is less compared to the ideal
gas
since Preal < Pideal
2
the term pressure need to be corrected by adding coefficient 2a
n
V
n=number of moles
V = volume
PV = nRT
Value of b :
• b is a constant to represent the volume occupied
by the molecules.
molecule at
the surface
molecule within
the liquid
√ these intermolecular attractive forces will
pull the molecules into the liquid
√ Thus, cause the surface to stretch and
tighten
√ the stronger the intermolecular attractive
forces, the higher the surface tension
3. Viscosity
is a measure of the resistance of a liquid
to flow
• Intermolecular forces
1. Atmospheric pressure
W hen the external atmospheric pressure is
low, liquid will boil at a lower temperature
2. Intermolecular forces
A substance with weak intermolecular forces
can easily vapourise and the system requires
less heat to achieve atmospheric pressure,
thus it boils at a lower temperature.
5.3 Solid
OBJECTIVE…
(a) State the properties of solid.
(b) Explain the process of:
- freezing - sublimation
- melting - deposition
(c) Differentiate between amorphous and crystalline
solids.
(d) Describe the types of bonding and the
interparticle/intermolecular forces involved in the
following crystalline solids using appropriate examples.
i. metallic iii. molecular covalent
ii. ionic iv. giant covalent
Properties of solid
liquid
sublimation
deposition
solid gas 5
Melting (Fusion) Process
Solid is changing into a liquid
When a solid substance is heated :
- its particles gain energy
- therefore able to vibrate more rapidly
- at certain temperature, the kinetic energy is higher
enough to overcome the intermolecular forces of
attraction between solid particles.
– the particles are free to move and the solid start to
melt
• Melting point – the temperature at which solid and
liquid coexist in equilibrium
Freezing (Solidification) Process
Deposition Process
•The process where molecules from vapour state
change to the solid state.
•The opposite process of sublimation
Types of Solid
1. Metallic solid
Close packed structure
Composed of atoms of the same metal linked
together by metallic bond
The properties of metal:
– High electrical and thermal conductivity
– Lustre
– Ductile and malleable
Examples : all metallic elements : Na, Mg, Fe
2. Ionic solids
consist of ions (cation & anion) held together by ionic
bonds
Physical properties of ionic solid:
- High melting point
- Hard but brittle
- Does not conduct electricity in the solid state but
does conduct electricity in molten state or in
aqueous state.
Example: NaCl, CsCl
3. Molecular covalent solid
composed of molecules held together by
intermolecular forces (van der Waals
and/or hydrogen bonds)
Example : iodine [I2 (s) ]
4. Giant covalent solids
very large molecules / gigantic structure
8/16/11
Regions of the diagram
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 0.01°C 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) Phase Diagram of CO2
B C
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
ANOMALOUS BEHAVIOR OF H2O
b) a reversible reaction
- occurs in both direction
i.e (forward & reverse reaction)
6.1.1 A non-reversible reaction
Example 1
[N2O4] at equilibrium
• Consider:
aA (g) + bB (g) ⇌ cC (g) + dD (g)
[C]c[D]d
Kc =
[A]a[B]b
• Kc is known as equilibrium constant
Concentrations of species are expressed in
molar.
Table 6.1
a) Homogeneous equilibrium
Homogenous equilibrium applies to reactions in
which all reacting species are in the same
phase.
b) Heterogeneous equilibrium
A system in which the reactants and products
are not in the same phase.
6.7 Homogeneous Equilibrium System
Example 5
CH3COOH (l) + CH3OH (l) ⇌ CH3COOCH3 (l) + H2O (l)
Kc=
Example 6
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
1. SO3 (g) ⇌ SO2 (g) + ½ O2 (g) Kc1 = [SO2] [O2]1/2
[SO3]
2. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) Kc2 = [SO3]2
[SO2]2 [O2]
Example 9
Find the relationship between Kc1 and Kc2 for the
following equilibrium equations.
[SO3]
[SO2]2 [O2]
Example 10
2
PNO
PO = 2
Kp 2
2
PNO
= 347 atm
6.7.3 Relationship between Kp and Kc
Consider
aA (g) + bB (g) ⇌ cC (g) + dD (g)
[C]c[D]d
Kc =
[A]a[B]b
Kc = Kp (RT) (a + b) – (c+d)
Kp = Kc (RT) (c + d) – (a+b)
Kp = Kc (RT)Δn
1. The equilibrium concentrations for the reaction
between carbon monoxide and chlorine to form
COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054
M, and [COCl2] = 0.14 M. Calculate the
equilibrium constants Kc and Kp.
Kp = Kc(RT)n n = 1 – 2 = -1
[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]
[CH3COO-][H3O+]
Kc =
[CH3COOH]
Unit : M
2. CH3COOH (aq) + C2H5OH (aq)⇌ CH3COOC2H5 (aq) + H2O (l)
Carboxylic Alcohol Ester
acid
[CH3COOC2H5]
Kc =
[CH3COOH] [C2H5OH]
3. CaCO3 (s) ⇌ CaO (s) + CO2 (g)
[CaO][CO2]
K‘c =
[CaCO3]
[CaCO3] = constant
[CaO] = constant
Kc = [CO2]
Kp = PCO2
CaCO3 (s) ⇌ CaO (s) + CO2 (g)
PCO2 = Kp
Kp = Kc(RT)n n = 2 – 0 = 2
T = 295 K
Kc = 0.0702 atm2
(0.08206 atm L mol–1 K–1 x 295 K )2
1
1 = = [NOBr]2
Kc [NO]2 [Br2] [NO]2 [Br2]
[NOBr]2
1 ½ [NOBr]
= = Kc ’
Kc [NO] [Br2] ½
Kc ’ = 1 ½
Kc
Kc ’ = 1 ½
1.0 x 10–3 M
= 31.6 M-½
49.5 = (2x)2
(0.0200 – x) (0.0200 – x)
7.036 = 2x
0.0200 - x
x = 0.0156
H2 (g) + I2 (g) ⇌ 2HI (g)
[ ]0 / M 0.0200 0.0200 0
Δ[ ] / M -x -x +2x
[H2] = 0.0044 M
[I2] = 0.0044 M
[HI] = 0.0312 M
8. A 1.000-L flask is filled with 1.000 mol of H2 and
2.000 mol of I2 at 448°C. The value of the
equilibrium constant, Kp for the reaction,
PH = nH RT = (1.000)(0.08206)(721)
2 2
V 1.000
= 59.19 atm
PI = nI2 RT = (2.000)(0.08206)(721)
2
V 1.000
= 118.4 atm
H2 (g) + I2 (g) ⇌ 2HI (g)
P0 59.19 118.4 0
ΔP -x -x +2x
P⇌ 59.19 - x 118.4 - x +2x
Kp = PHI
2
⇒ 50.5 = (2x)2
PH2 P I2 (59.19 – x) (118.4 – x)
ΔC ΔC = changes in concentration
α =
C0 C0 = initial concentration
C0 / M a 0 0
ΔC / M -x +x +x
C⇌ / M a-x +x +x
x
α =
a
9. The concentration of H+ ion measured for HCOOH
0.5 M is 0.0089 M. What is the degree of dissociation
of the compound?
a = 0.5 x = 0.0089
HCOOH ⇌ H+ + HCOO–
C0 / M 0.5 0 0
ΔC / M -0.0089 +0.0089 +0.0089
C⇌ / M 0.5-0.0089 0.0089 0.0089
= 0.4911
x 0.0089
α = = = 0.0178 = 1.78%
a 0.5
6.2.7 Predicting the direction of reaction
[Br]2
Qc = = (0.012)2 = 2.29 x 10–3
[Br2]
0.063
Qc > Kc Equilibrium position shifts
from right to the left.
Br2 (g) ⇌ 2Br (g)
C0/M 0.063 0.012
ΔC/M +x - 2x
C⇌/M 0.063 + x 0.012 - 2x
[Br]2
Kc =
[Br2]
(0.012 – 2x)2
1.1x10-3 =
0.063 + x
4x2 – 0.048x + 1.44x10-4 = 6.93x10-5 + 1.1x10-3x
x = 0.0105 x = 1.78x10-3
Kc = [HI]2
[H2] [I2]
54.0 = (1.97 – 2x)2 7.35 = 1.97 – 2x
(0.200 + x) (0.200 + x) 0.200 + x
x = 0.0535M
6.3 Factors affecting the equilibrium
position
The position of equilibrium in a system is affected
by:
a) concentration
b) pressure
c) temperature
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)
Example:
• Consider the following system:
N2O4(g) 2NO2(g) ΔH = +57 kJ
Disturbance:
High
Low temperature temperature
C) Effect of Pressure
Example:
Consider the following system at equlibrium
2SO2(g) + O2(g) 2SO3(g)
• When SO2 gas is added to the system, the partial
pressure of SO2 increases (which means [SO2]
increases)
• Equilibrium shifts to the right to reduce the effect
of high concentration of SO2.
ii. Changing the volume of the container:
Kp = Kc(RT)Δn Δn = 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 10–3 M
(b)(i) Does not change
(the partial pressure of CO2 is not affected by
the removal of SOLID CaO from the system).
1
7.1 ACIDS AND BASES
1. Arrhenius theory
2. Bronsted-Lowry’s theory
3. Lewis theory
2
Theory of Acids and Bases
1. Arrhenius Theory
Acid:
any substance that produces hydrogen ion (H+) or
hydronium ion (H3O+) when dissociating in water.
Example:
3
Base:
any substance that produces hydroxide ions (OH-)
when dissociating in water.
Example:
4
2. Bronsted-Lowry Theory
Acid:
any substance that can donate a proton, (H+) to
other substance
Example:
5
Base:
any substance that can accept a proton from
other substance
Example:
NH3 (aq) + H2O (l) NH4+ (aq) + OH (aq)
base
6
Conjugate Acid-base Pairs
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.
7
Example
8
Exercise
1. In the following reactions, identify the acid-base conjugate
pairs.
9
c. HBr(aq) + NH3(aq) NH4+(aq) + Br (aq)
acid base conjugate conjugate
acid base
10
2. Write the conjugate base formula for the following acids.
a) HS d) H3PO4
b) HCN e) H3O+
c) N2H5+ f) CH3NH3+
Answer :
acid 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
3. Write the conjugate acid formula for the following bases.
a) HS- d) NH3
b) C6H5COO e) H2O
c) OH f) H2PO4
12
3. Lewis Theory
Acid:
a substance that can accept a pair of electrons to
form a covalent bond.
13
Base:
a substance that can donate a pair of electrons to
form a covalent bond.
14
Example
15
Exercise
Classify each of the following species as Lewis acid
or Lewis base.
ii. AlCl3
Lewis acid
iii. BCl3
Lewis acid
iv. Ag+
Lewis acid
v. I-
Lewis base
16
Strength of Acids and Bases
[ ]dissociated
% dissociation = 100%
[ ]initial
[ ]dissociate d
Degree of dissociation, =
[ ]initial
17
Strong Acid
Strong acid is an acid that ionizes completely in
water.
18
Example : for 0.10 M HCl
[ ]i 0.10 0 0
Δ - 0.10 + 0.10 + 0.10
[ ]f 0.00 0.10 0.10
19
[HCl]dissociated
% dissociation = 100%
[HCl]initial
0.10=
100%
0.10
= 100 %
[HCl]dissociated
Degree of dissociation, =
[HCl]initial
0.10 =
0.10
= 1.00
20
The strong acids are ...
21
Strong Base
Strong base is a base that ionizes completely in
water.
H2O
NaOH (aq)
Na+ (aq) + OH (aq)
[ ]i 0.50 0 0
Δ - 0.50 + 0.50 + 0.50
[ ]f 0.00 0.50 0.50
22
[ NaOH ]dissociated
% dissociation = 100%
[ NaOH ]initial
0.50=
100%
0.50
= 100 %
[ NaOH ]dissociated
Degree of dissociation, =
[ NaOH ]initial
0 .50=
0 .50
= 1.00
23
The strong bases...
24
Weak Acid
Weak acid is an acid that only ionizes partially in
water
Example: CH3COOH, HCOOH
<1
25
Acid dissociation constant expression, Ka
[A ][H3O ]
Ka =
[HA]
26
The weak acids are ....
27
Weak Base
Weak base is an base that only ionizes partially in
water
Example: NH3, N2H4
<1
28
Base dissociation constant expression, Kb
[BH ][OH ]
Kb =
[B]
29
The weak bases are ...
◦ Ammonia (NH3)
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
[ ]i 0.10 0 0
Δ -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
Ka = [H 3O ] [HCOO ]
[HCOOH]
34
Try this…
1. Acid dissociation constant, Ka for hydrofluoric
acid HF at 25 C is 6.8104 M. For a solution of
0.20 M HF, calculate:
a. the concentration of hydronium ion at
equilibrium
b. degree of dissociation
35
Water and the pH Scale
a. The Water Ionization Constant, Kw
◦ When water molecules ionized, transferring a
proton from one water molecule to another
producing a hydroxonium and hydroxide
ion.
36
2H2O (l) H3O+ (aq) + OH (aq)
37
For pure water, at 25C,
Kw = H3O+ OH
= (1 x 10-7) (1 x 10-7)
Kw = 1 x 10-14 M2
Note:
Temperature ↑, Kw ↑ because the dissociation
of water is an endothermic process
38
a. The pH Scale
pH = log H3O+
39
In similar way, pOH is the negative logarithm of
the hydroxide ion concentration.
40
In pure water,
pH = pOH = log (1 x
10-7 )
pH = pOH = 7
pH + pOH = 14
41
At 25 oC,
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. The Ka for benzoic acid, (C6H5COOH) is 6.5x10-5.
Calculate the pH of a 0.25 M benzoic acid solution.
(2.39)
48
1. Calculate pH for the following solution.
Answer
a. 0.55 M CH3COOH (Ka = 1.8x10-5) 2.5
b. 0.23 M NH3 (Kb = 1.8x10-5) 11.31
c. 0.15 M HCl 0.82
d. 0.20 M KOH 13.3
e. 0.45 M HCN (Ka = 4.9 x 10-10) 4.8
49
SALTS
50
1) Neutral salts
Produced when strong acid reacts with strong base.
e.g
HCl + NaOH NaCl + H2O
neutral salt
51
So, pH of a solution depends on the ionization of water
pH = 7
52
SALT HYDROLYSIS
Salt hydrolysis is a chemical reaction between anion
or cation of a salt with water molecules.
53
2) BASIC SALTS
Normally is produced from the reaction of weak acid
and strong base.
produce OH- when hydrolyzed
eg : CH3COONa(aq) Na+ (aq) + CH3COO- (aq)
54
Hydrolysis of CH3COO- :
55
Example
56
3) ACIDIC SALTS
Normally is produced from the reaction of strong
acid and weak base.
produce H3O+ when hydrolysed.
Eg.
NH4Cl(s) NH4+(aq) + Cl(aq)
Cl- : comes from a strong acid
(does not hydrolyzed)
NH4+ : comes from weak base and
undergoes hydrolysis
57
Hydrolysis of NH4+ :
58
Example
59
BUFFER SOLUTION
60
ACIDIC BUFFER SOLUTION
Has pH < 7.
Example:
A solution of CH3COOH and CH3COONa
61
The dissociation reactions are:
62
Equilibrium of acid shifts backward, less
CH3COOH dissociates.
63
BUFFER’S ACTION
Since buffer solution contains CH3COOH that acts
as acid and the conjugate ion CH3COO- that acts
as base, buffer solution will maintain its pH by
performing reactions as follows:
65
CALCULATION OF pH OF BUFFER SOLUTION
The pH is obtained by referring to the equilibrium
dissociation of a weak acid, HA.
HA H+ + A-
66
We can write the acidic concentration constant,
[ H ][ A ] Ka[HA]
Ka or [H+] =
[ HA ] [A ]
Henderson-Hasselbalch equation
67
Example
68
BASIC BUFFER SOLUTION
Has pH > 7
69
NH4Cl dissociates completely and produce high
concentration of NH4+ ions
70
BUFFER’S ACTION
Buffer solution maintains its pH by performing
reactions as follow :
71
(i) Adding a small amount of acid to the solution
72
(ii) Adding a small amount of base to the solution
73
CALCULATION OF pH OF BUFFER SOLUTION
74
The base dissociation constant, Kb
[BH ][OH ] [ B]
Kb = or [OH-] = Kb
[B] [ BH ]
75
Example
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
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
7.2 ACID-BASE TITRATIONS
Titration
◦ a method for determining the
concentration of a solution using
another solution (known concentration),
called standard solution
Titration Curve
◦ a graph of pH versus volume of titrant
79
Titration apparatus
Titrant
Analyte
80
The equivalence point
Indicators
Colour
Indicator In Acid In Base pH Range *
83
Strong acid-strong base titration curves
84
* The pH rises sharply
when the mole of OH-
that have been added
nearly equal the mole
of H3O+ .
85
* An additional drop or two of
base neutralises the
final tiny excess of acid and
introduces a tiny excess of
base, so pH jumps 6 to 8 unit.
86
Weak acid-strong base titration curves
87
* A gradually rising portion
of the curve, called the
buffer region, appears
before the sharp rise to
the equivalence point.
88
* The pH at the
equivalence point > 7.0.
The solution contains the
basic salt.
89
Weak base-strong acid titration curves
90
* After the buffer region,
the curve drops vertically
to the equivalence point.
91
How to sketch a titration curve
Steps :
1. Calculate the initial pH of the solution
- identify the analyte (solution in the conical
flask). Whether strong acid, weak acid,
strong base or weak base.
92
3. pH jump (steep portion / sharp portion)
- depends on the type of the titration
Type pH jump
94
Step 2 : at equivalence point
- pH equivalence:
- the solution is NaCl (aq)
- both Na+ and Cl- do not hydrolyse
- therefore pH = 7.0
- Volume equivalence:
n HCl = n NaOH
MHCl VHCl = MNaOH VnaOH
VNaOH = 0.1 x 25 = 25 mL
0.1
95
Step 3 :
Type of titration : strong acid-strong base
pH jump : 3 – 11
Step 4 :
Titrant is a strong base, NaOH.
NaOH (aq) Na+ (aq) + OH (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
3
VNH = 0.2 x 25 = 50 mL
3
0.1
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
How to determine the suitable indicator for titrations
Choose an indicator which the endpoint pH range lies on the
steep portion of the titration curve.
103
The solubility of a salt is the amount of solid
that dissolved in a known value of saturated
solution.
104
THE SOLUBILITY PRODUCT CONSTANT, Ksp
105
Consider the equilibrium system below :
Kc = [M+] [X-]
[MX]
106
Soluble salt such NaCl and KNO3 has an
extremely high value of Ksp .
107
Example
a) Ca3(PO4)2 b) Ag2CO3
108
Example
109
Example
110
Example
111
Predicting the formation of a precipitate
Precipitate is an insoluble solid formed in and
separates from the solution.
112
The solubility equilibrium equation for a slightly
soluble salt, MA :
MA (s) M+ (aq) + A- (aq)
113
Three possible situations:
Q < Ksp;
Solution is not saturated.
Solid will dissolve and no precipitate formed.
Q = Ksp;
Saturated solution formed.
System is in equilibrium.
Q > Ksp;
Solution is supersaturated;
Ions will form precipitate until the ionic concentration
product of the system equals the Ksp (until the system
reaches equilibrium).
114
Example
115
Example
116
COMMON ION EFFECT
117
Example
118
The equilibrium system is:
119
Example
a. liquid water
b. 0.05 M of silver nitrate solution.
(Ksp AgCl = 1.6 x 10-10)
120
9.0 THERMOCHEMISTRY
Concept of Enthalpy
Important Terms
Heat is energy transferred between two bodies of
different temperatures
reactants
enthalpy
H = -ve
products
reaction pathway
Enthalpy of combustion
Enthalpy of atomisation
Enthalpy neutralisation
Enthalpy hydration
Enthalpy solution
Enthalpy of Formation, ∆Hf
The change of heat when 1 mole of a compound is
formed from its elements at their standard states.
H subl
q = mc∆T
q = C∆T
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ
mole of H2 = 0.100
2.016
= 0.0496 mol
moles of H2O = mole of H2
= 284 kJ
∆Heat of reaction, ∆H = - 284 kJ mol1
Example 2
Solution
Heat released Heat absorbed by Heat absorbed by
= +
aluminium water
calorimeter
q = mwcwΔT + mcccΔT
= (1700.0 g)(4.18 Jg-1 °C-1)(2.8 °C) +
(3087.0 g)(0.553 Jg-1 °C-1)(2.8°C)
= 24676.71 J
= 24.7 kJ
HESS’S LAW
Hess Law
Hess’s Law states that when reactants are converted to
products, the change in enthalpy is the same whether the
reaction takes place in one step or in the series of steps.
The enthalpy change depends only on the nature of the
reactants and products and is independent of the route
taken.
A H 1 B
H 2
H 3
C
i.C O CO H - 393kJmol- 1
(S) 2( g ) 2( g )
ii.H 1 O H O H -286kJmol- 1
2( g ) 2 2( g ) 2 ( g)
iii.C H 7 O 2CO 3H O H -1560kJmol -1
2 6( g ) 2 2( g ) 2( g ) 2 ( g)
Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C O CO H - 393kJmol- 1
(S) 2( g ) 2( g )
ii.H 1 O H O H -286kJmol- 1
2( g ) 2 2( g ) 2 ( g)
iii.C H 7 O 2CO 3H O H -1560kJmol -1
2 6( g ) 2 2( g ) 2( g ) 2 ( g)
ii. Write the enthalpy of formation reaction for C2H6
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.
HO2 = 3(-286)
HO1 2O2(g) 3/2 O2(g)
7/2 O2(g)
= 2(-393)
HO3 = - (-1560)
H f
Born-Haber
Cycle
Lattice Energy, Hlattice
is the energy required to completely separate one mole of a
solid (ionic compound) into gaseous ions
e.g:
NaCl(s) Na+(g) + Cl-(g) Hlattice = +771 kJ mol-1
(lattice dissociation)
He
y a
rg to
Ene fH
e yd
ttic ra tio
La n
Heat of Solution
HaCl
Na(g) + ½ Cl2(g)
+ve Lattice energy
HaNa
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:
Construct a Born-Haber cycle to explain why ionic compound
NaCl2 cannot form under standard conditions. Use the data
below:
i. Enthalpy of sublimation of sodium = +108 kJmol-1
ii. First ionization energy of sodium = +500 kJmol-1
iii. Second ionization energy of sodium = +4562 kJmol-1
iv. Enthalpy of atomization of chlorine = +121kJmol-1
v. Electron affinity of chlorine = -364 kJmol-1
vi. Lattice energy of NaCl2 = -2489 kJmol-1
Electrochemistry
Electrochemistry
Is the study of the relationship between electricity
and chemical reaction
Reduction
REDOX REACTION
Oxidation
Cu2+ + 2e- Cu
Oxidation no.
Electrochemical reaction consists of reduction
and oxidation.
These two reactions are called ‘half-cell
reactions’
The combination of 2 half reactions are called
‘cell reaction’
Example
Reduction : Cu2+(aq) + 2e- Cu(s)
Half-cell
Oxidation : Zn(s) Zn2+(aq) + 2e- reaction
Overall cell 2+ 2+
reaction :
Cu (aq) + Zn(s) Cu(s) + Zn (aq)
Cells
There are 2 type of cells
Electrochemical Electrolytic
Cells Cells
where chemical reaction Uses electricity to
produces electricity produce chemical
reaction
Also called;
Galvanic cell or Voltaic cell
Chemical Electrical Electrical Chemical
Energy Energy Energy Energy
Component and Operation of
Galvanic cell
Consists of :
1) Zn metal in an aqueous solution of Zn2+
2) Cu metal in an aqueous solution of Cu2+
Voltmeter
Zn Cu
electrode electrode
Zn2+ Cu2+
CuSO4(aq)
ZnSO4(aq)
solution
solution
Salt
bridge
What happens at the zinc electrode ?
Zinc is more electropositive than copper.
Tendency to release electrons: Zn > Cu.
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.
What happens at the copper electrode ?
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.
What happened if there is no salt bridge?
Zn Cu
e
e
e e
Zn2+ e e Cu2+
ZnSO4(aq) CuSO4(aq)
E = +1.10 V
Zn - + Cu
e
Zn2+ e
ZnSO4(aq) Cu2+ CuSO4(aq)
Salt bridge
(KCl)
How does the cell maintains its electrical neutrality?
anode cathode
oxidation reduction
spontaneous
redox reaction
half 19.2
Cell notation
Cell notation
Exercise
For the cell below, write the reaction at anode
and cathode and also the overall cell reaction.
Cell notation
Zn (s) | Zn2+(aq) || Cr3+ (aq) | Cr (s)
Anode : 3 Zn(s) → 3Zn2+(aq) + 6e
2e- X3
Cathode : 2 Cr3+(aq) + 6e
3e- → 2Cr(s) X2
Overall cell 3Zn(s) + 2Cr3+(aq) + → 3Zn2+ (aq) +2Cr(s)
reaction:
The difference in electrical potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
measured by a voltmeter
• cell potential
= +0.34 – (-0.76)
= +1.1 V
Zn2+ (aq) + 2e- Zn (s) E0 = -0.76V
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:
H2 gas
at 1 atm
Pt
H+ (aq) electrode
1 M
The standard reduction of SHE is 0 V
Standard reduction potential of Zinc half cell is
measured by setting up the electrochemical
cell as below.
E0 = +0.76
- V + E0 = 0
+
-
H2 (g), 25oC,1 atm.
Zn e
e
e H+(aq),1 M
2+
Zn e
ZnSO4(aq) Pt
1M
Standard Electrode Potentials
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
+ V- E0 = 0
-
+ H2 (g) 25oC
1 atm.
Cu
H+(aq)
Cu2
1M
CuSO4(aq) Pt
1M
Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)
Anode (oxidation): H2 (1 atm) 2H+ + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 + Cu2+ Cu (s) + 2H+
0 = E0
Ecell 0
cathode - Eanode
0 = E 0 2+
Ecell 0
Cu /Cu – EH +/H2
0 2+
0.34 = ECu /Cu - 0
0 2+
ECu /Cu = 0.34 V
The direction of half-reaction of SHE depends on the
other
half-cell connected on it.
The cell notation for SHE is either:
H+(aq) | H2(g) | Pt(s) when it is cathode
= +0.34 + (+0.76)
= +1.10 V
Half-cell equation at:
or
Answer :
L < X < Y
Example
Calculate the E0 cell for the reaction ::
Mg(p) | Mg2+(ak) || Sn4+(ak),Sn2+(ak) | Pt(p)
Given :
E0cell = Ecathode - Eanode
Mg2+(ak) + 2e→ Mg(p) Eθ = -2.38 V
=+0.15- (-2.38)
Sn4+(ak) + 2e → Sn2+(ak) Eθ= +0.15 V
=+2.53V
Oxidation : Mg(p) → Mg2+(ak) + 2e Eoox = +2.38 V
Reduction : Sn4+(ak) + 2e → Sn2+(ak) Eo = +0.15 V
Mg(p) + Sn4+(ak) → Mg2+(ak) + Sn2+(ak) Ecell = +2.53 V
Eθcell = E o red + E o ox
= +2.38 + 0.15
= +2.53 V
Exercise
A cell is set up between a chlorine electrode and a
hydrogen electrode
E0cell = +1.36 V
Pt Pt
H+(aq), 1M Cl-(aq), 1M
1. Show the process occur at anode and
cathode
- Half-cell reaction
2. Overall reaction
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
Spontaneous & Non-Spontaneous reactions
- Redox reaction is spontaneous when
Ecell is +ve.
- Non spontaneous is when Ecell is –ve.
spontaneous
Pb2+(aq) + 2Cl-(aq) → Pb(s) + Cl2(g)
Reduction
Pb2+(aq) + 2Cl-(aq)
Pb2+(aq) + 2Cl-(aq) →
→ Pb(s) + Cl (g)
→Pb(s)
Pb(s)+ Cl+2(g)
Cl2 (g)
Oxidation
cathode: Pb2+(aq) + 2e → Pb(s) Eo = -0.13 V
anode: 2Cl-(aq) → Cl2(g) + 2e Eoox = -1.36
= -1.48 V
Non-spontaneous
No Reaction
Example :
Predict whether the following reactions occur
spontaneously :
2Ag(s) + Br2(aq) 2Ag+(aq) + 2Br-(aq)
0 +
EAg = +0.8 V
/Ag standard reduction
0
EBr potential
2 /Br
- = +1.07 V
Answer :
2Ag(s) 2Ag+(aq) + 2e Eθox = - 0.80 V
[ product ]x
= Q
[ reactant]y
Answer
= +1.10 V – (-0.0385)
= +1.139 V
At equilibrium:
~ No net reaction occur (Q=K)
~ Ecell = 0
0 = Eocell – 0.0592
log K
n
Eθcell = 0.0592
log K
n
Example 2
Calculate the equilibrium constant (K) for the
following reaction.
Answer
At equilibrium, E cell = 0
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- M+,H+
Anion Cation
A Positive electrode
n The electrode which is connected to the
o positive terminal of the battery
d
Oxidation takes place
e
Electrons flow from anode to cathode
C
a Negative electrode
t The electrode which is connected to the
h negative terminal of the battery
o Reduction takes place
d
e
Electrode
as circuit connectors
as sites for the precipitation of insoluble
products
example: Platinum , Graphite (inert electrode)
Electrolyte
Reduction :
2H2O (l) + 2e- H2 (g) + 2OH- (aq) E0 = -0.83 V
Oxidation :
2H2O (l) 4H+ (aq) + O2 (g) + 4e- E0 = -1.23 V
Predicting the products of electrolysis
Solution
Na2SO4 aqueous solution contains Na+ ion, SO42- ion
and water molecules
On electrolysis,
the cathode attracts Na+ ion and H2O molecules
Anode
S2O82- (aq) + 2e- 2SO42- (aq) E0 = +2.01 V
O2 (g) + 4H+ (aq) + 4e- 2H2O (l) E0 = +1.23 V
mαQ
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
Mr for Cu = 63.5
Mass of Copper deposited = 0.014 x 63.5
= 0.889 g
11.0 REACTION KINETICS
Objectives:
industrial process
-Time
-Optimum yield
-Optimum conditions
control over reaction,
obtain products economically,
using optimum conditions
Rate of reaction
• Reaction rate is the change in the concentration
of a reactant or a product with time.
• Unit of rate (mol L-1 s-1)
1
• rate
Time
Example; A B
time
[B] ↑
d[A]
rate = -
dt
d[B]
rate =
dt [A] ↓
Rate of reaction
Solution:
1 d[HI] d[H 2 ] d[I 2 ]
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)
Rate α [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.
rate = k [F2][ClO2] 1
The units of rate constant, k
A Products
Rate, r = k [A]x
Rate = k [A]0
Rate = k
M s-1
Unit k =
M
= s-1
iii) Second order
Rate = k [A]2
rate
k=
[A]2
M s-1
Unit k = = M-1 s-1
M2
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
k= rate Ms-1 M-1 s-1
Unit k = =
[S2O82-]1[I-]1 M2
The order of reaction
For reaction
A 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
Assume [A]i = 1.0M
Rate = k (1.0M)
Rate = k (2.0M)
= 2k(1.0M)
hence
Rate = 2k[A]
Doubling the [A] will double the rate of reaction.
Therefore this reaction is first order with respect to A
iii) If x = 2
Rate = k[A]2
= 4k(1.0 M)
hence
Rate = 4k[A]
Doubling [A], the rate will increase by a factor of 4.
Therefore the reaction is second order with respect to A
Example
Initial Reactant
Concentrations (molL-1) Initial Rate
Experiment (M s-1)
O2 NO
rate = k [O2]m[NO]n
6.40x10-3Ms-1 2.20x10-2mol/L m
=
3.21x10-3Ms-1 1.10x10-2mol/L
2= 2m , m = 1 ;
The reaction is first order with respect to O2
Rate = k[O2][NO]2
Exercise:
ClO2(aq) + 2OH- (aq) products
The results of the kinetic studies are given below.
exp [ClO2] [OH-] Initial rate,
M M Ms-1
1 0.0421 0.0185 8.21 1 0-3
2 0.0522 0.0185 1.26 1 0-2
3 0.0421 0.0285 1.26 1 0-2
Objectives:
1.Write the rate law for zero order, 1st order and
2nd order reaction
2. Define half-life.
3. Draw the respective graphs for the different
order reactions
4. Solve quantitative problems.
Integrated rate equations
Zero Order Reaction
A product
[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
[A]o – [A] = kt
[A]o – [A]
y = mx + c
t [A]
Half-life (t½)
Half life (t½) is the time required for the concentration of a reactant to decrease
to half of its initial value.
[A]0 - [A] = kt
[A]0 – [A]0 = kt1/2
2
Solving for t1/2 gives
t1/2 = [A]0
2k
First Order Reactions
unit k = M s-1
M
= s-1
Rate = k[A]
y = mx + c
Rate
Ms-1
[A] ,M
For first order reaction,
Rate = k[A]
- d[A] substituting
= k[A]
dt t = 0, [A]=[A]0
- d[A]
= k dt
[A] - ln [A]0 = k(0) + c
c = ln[A]0
- d[A]
∫ = ∫ k dt
[A] -ln [A] = kt – ln[A]0
- ln [A] = kt + c
[A]0
ln = kt
[A]
Characteristic graphs of 1st order reaction
[A]0
ln ------ = kt
[A]
t
ln[A]
ln[A]o
ln[A]o
[A]
t t
Example
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
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) [H2O2]0
ln = kt
[H2O2]
0.882
ln = 3.66 x 10-3 s-1 x t
0.600
ln 1.47 = 3.66 x 10-3 s-1 x t
ln 1.47
t=
3.66 x 10-3
= 105.26 s
b) [H2O2]0
ln = kt
[H2O2]
0.882
ln = 3.66 x 10-3s-1x 225 s
[H2O2]
[H2O2] = 0.387 M
Exercise,
CH2
CH2 CH2 CH3-CH=CH2
No. of
half-lives [A]o = 8 M
1 4
2 2
3 1
4 1/2
t½ = 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
Example
A product
Where
d[A]
Rate = - = k[A]2
dt
To obtain the units of k
rate
k =
[A]2
M/s
Unit k =
M2
= M-1 s-1
1 1
= - + kt
[A] [A]0
Characteristic graphs for second order reaction
Rate = k [A]2
rate
[A]
rate
[A]2
Graphs for second order reaction
1 1
[A] = + kt
[A] [A]o
1/[A]o
t t
2nd –order reaction, r = k[A]2
If [A] doubles,
r2 = k (2[A])2
= k ( 4 [A]2 )
= 4 k [A]2
=4r
1 1
= + kt
[A] [A]0
[A]= [A]o
Substituting t = t1/2
2
1 1
= + kt1/2
[A]0 [A]0
2
1
t1/2=
k[A]0
Detemination of half-life using graph for second order reaction
[A]0
1
t1/2=
k[A]0
[A]0/2
[A]0/4
[A]0/8
x 2x 4x t
Example
Iodine atoms combine to form molecular iodine in
the gaseous phase
1 1
= + kt
i)
[A] [A]0
1 1
= + (7.0 x 109 x 2 x 60 )
[A] [0.086]
= 8.4 x 1011
= 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,
time, t/min 0 10 20 30 40 50 60
[N2O5] x 10-4 M 176 124 93 71 53 39 29
180
160
140
120
[N2O5] x 100
10-4 /M
80
60
40
20
10 20 30 40 50 60 70 80
Time ( min)
i) Based on the above graph,
The half life for the reaction is a constant and does not depend on the
initial concentration of N2O5
ln2
ii) = 0.03 min-1
k=
20 min
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions
Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k
[A] [A]
[A] [A]2
Integrated rate law Integrated rate law Integrated rate law
[A]0 – [A] = kt ln([A]0 / [A]) = kt 1/[A] – 1/[A]0 = kt
[A] t1/2 = [A]0/2k [A] ln[A] [A] 1/[A]
[A]0 ln[A]0
1/[A]0
t t t t t
[A]0 - [A]
ln([A]0 / [A]) 1/[A] – 1/[A]0
Orientation is important
Transition State Theory
Activated complex
Transition state
Ea (Forward reaction)
Ea (reverse reaction)
H
Ea
(reverse reaction)
Ea
(forward reaction)
Product
H
Reactant
A Reaction profile: endothermic reaction
Ea
H
• 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
4 particle system
(2 and 2) 4 collision
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 y
Reaction rate = k [ A ] [ B ] …
(A & B = reactants)
(x & y = rate order)
-Ea∕
k = A 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:
-Ea∕
k = A e RT
1/T (K-1)
B) TEMPERATURE
Ea
RT
k Ae
Ea
Natural log both ends… RT
ln k ln( A .e )
Ea
RT
ln k ln A ln( e )
Ea
ln k ln e ln A (But ln e = 1)
RT
Ea 1
Thus… ln k ( ) ln A
R T
See the linear relationship…? y = m x + C
B) TEMPERATURE
Graph Representation Of The Arrhenius Equation
• Plotting a ln k vs 1/T graph would show a clearer
relationship between k (Rate constant) and
temperature
Ea 1
ln k ( ) ln A
R T
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 Ea 1
ln k1 ( ) ln A ln k 2 ( ) ln A
and R T2
R T1
Rearranging the equations would give…
Ea 1 Ea 1
ln k 1 ( ) ln A ln k 2 ( ) ln A
R T1 R T2
Since “A” is a constant…
E 1 E 1
ln k 1 a ( ) ln k 2 a ( )
R T1 R T2 k1 Ea 1 1
ln ( )
Ea 1 Ea 1 k2 R T2 T1
ln k1 ln k 2 ( ) ( )
R T2 R T1
Exercise: the Activation energy
The decomposition of hydrogen iodide,
2 HI (g) H2(g) + I2(g)
has rate constants of 9.51 x 10-9 L mol-1 s-1 at 500 K and
1.10x10-5 L mol-1 s-1 at 600 K. Find Ea.
k1 Ea 1 1
ln ( ) 1.10 10 5 1 1 1
k2 R T2 T1 Ea (8.314 ) ln( 9
)( )
9.51 10 600 500
k1 1 1
E a R ln( )( ) 1
k 2 T 2 T1
Ea = 1.76 x 105 J/mol = 176 kJ/mol
C) CATALYST
x y
Reaction rate = k [ A ] [ B ]
(A & B = reactants)
(x & y = rate order)
Ea 1
ln k ( ) ln A
R T
C) CATALYST
• When Ea decreases, k increases,
REACTION RATE increases
uncatalyzed catalyzed
Ea > E’a
Reaction pathway
D) PARTICLE SIZE
OCOCH3
COOH
CH2 NH S
C
N
O
COOH
penicillin (an antibiotic)
Cl CH Cl
CCl3
dichlorodiphenyltrichloroetane
(DDT- a pesticide component)
All organic compounds consist of carbon atom.
Properties of carbon atom:
-has 4 valence electrons.
-can form 4 covalent bonds.
C C C C C C
saturated unsaturated
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:
H H H H
C4H9Cl
Molecular H C C C C H
Formula H Cl H H
Expanded structure
Examples:
i) Alcohol (C2H6O)
H H
H C C OH
H H
i) CH3CH(Cl)CH2CH3 =
Cl
H2C CH2
ii) =
H2C CH2
3- Dimensional formula
( wedge – dashed wedge – line formula )
H C H
Br H H
C C C
or H Br or H H
H H H Br
H
Indication :-
:bonds that lie in the plane
:bonds that lie behind the plane
:bonds that project out of the plane
Classification of C atoms:
H C H
CH3
10 carbon
10 carbon
CH3
H C CH3
CH3
30 carbon
1
1
H H CH3 CH3
1 1
H C C C CH2 C CH3
H H H CH3
1
H H CH3 CH3
2
H C C C CH2 C CH3
2
H H H CH3
H H CH3 CH3
3 4
H C C C CH2 C CH3
H H H CH3
Question
CH3(CH2)CCl(CH3)2
H H CH3
H
C C CH
H H CH3
12.3 FUNCTIONAL GROUPS
AND HOMOLOGOUS SERIES
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.
Functional groups are important for three
reasons:
Functional Group
Class of Example
Compound
Structure Name
Alkane CH3-CH3
carbon-carbon
Alkene -C=C- double bond CH3CH=CH2
carbon-carbon
Alkyne -C C- triple bond CH3C CCH3
Aromatic Benzene ring -CH3
R-C=O CH3-C=O
Ketone R Carbonyl CH3
-C-O-C- CH3-C=O
Ester O Carboalkoxy OCH3
-C=O CH3-C=O
Acyl chloride Cl Cl
O O O O
Anhydride -C-O-C- CH3C-O-CCH3
NH2 CH C O CH3
CH2 O
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/
Stereoisomerism
Constitutional Isomerism
cis-trans other
isomerism diastereomers
Isomerism
is the existence of different compounds with
the same molecular formula but different
structural formulae.
• 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 CH3CCH3
CH3 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
CH3
1,2-dimethylbenzene 1,3-dimethylbenzene
1,4-dimethylbenzene
C6H13N
NH2
CH3 CH3
H2N
CH3
CH2NH2
NH2
3)Functional group isomerism
These isomers have different functional groups and
belong to different homologous series with the same
general formula.
Different classes of compounds that exhibit
functional group isomerism :-
General formula Classes of compounds
O O
propanone propanal
O O
propanoic acid methyl ethanoate
Exercise:
H H
CH3 H
H CH3
CH 3 CH 3
cis-1,2-dimethylcyclohexane
trans-1,2-dimethylcyclohexane
If one of the doubly bonded carbons has 2 identical
groups, geometric isomerism is not possible.
Example
H3C
CH3
C C
H3C
H
No cis – trans isomer
Lecture 6
12.4
Learning Outcomes:
Isomerism
At the end of the lesson the students should be able to
:
• Identify cis-trans isomerism of a given structural
formula.
• Define chirality centre and enantiomers.
• Identify chirality centre in a molecule.
• Explain optical activity of a compound.
• Draw a pair of enantiomers using 3-dimensional
formula.
• Define racemate.
• State the applications of chiral compounds in daily
life.
Enantiomer
Optical Isomerism
• Optically active compounds have the ability to
rotate plane-polarized light to the right
(dextrorotary) and to the left (levorotary)
• The angle of rotation can be measured with an
instrument called polarimeter.
Polarimeter
The requirements for optical isomerism :-
i) molecule contains a chiral carbon or chirality centre
or stereogenic centre (a sp3-hybridized carbon atom
with 4 different groups attached to it)
P
PQRS
C* *designates chiral centre
Q S
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
CH2CH3 CH2CH3
C* C
H3C H CH3
H
OH OH
enantiomers
ii) 2-hydroxypropanoic acid, CH3CHCOOH
OH
COOH COOH
H OH 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 plane-
polarized light.
Applications of chiral compounds in
daily life.
e.g:
Learning Outcomes:
At the end of the lesson the students should
be able to :
Explain covalent bond cleavage:
homolytic
heterolytic
Types of Covalent Bond Cleavage/Fission
X : X
X + X
free radicals
X X
b) Heterolytic cleavage
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
is an anion counterpart
a species with a negative charge on a carbon
atom.
Carbanion is formed in heterolytic cleavage.
example:
• (CH3)3C — Li (CH3)3C- +
Li+ carbanion
kation
b) Free Radical
A very reactive species with an unpaired electron.
Formed in homolytic cleavage.
Examples:
i)
free radicals
Cl
– Cl uv Cl● + Cl ●
ii)
C C ●C + ●C
iii)
H3C H 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.
Relative Stabilities of Carbocations,
Carbanions and Free Radicals
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
H H R R
H C H < H C R < H C R < R C R
- - - -
Methyl Primary Secondary Tertiary
anion 10 20 30
Increasing stability
Free-radical stability
Increasing stability
Reagents and sites of organic
reactions
A) Electrophile
Means ‘electron loving’.
An electron-deficient species and accepting
electron from an attacking nucleophile.
Can be either neutral or positively charged
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.
electrophilic sites are molecules with low
electron density around a polar bond
Examples:
i) ii)
+ - + -
-C = O (carbonyl) ; -C – X (haloalkanes)
iii)
+ -
-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 :
Addition
Substitution
Elimination
Rearrangement
I) Addition Reaction
a) Electrophilic Addition
b) 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 :
CCl4
CH3CH=CH2 + Br2 Room
CH3CHBrCH2Br
temperature
electrophile
b) Nucleophilic Addition
O CN
CH3 C CH3 + HCN CH3 C CH3
OH
II) Substitution Reaction
A reaction in which an atom or group in a
molecule is replaced by another atom or group.
Fe
catalyst
+ Br2 Br + HBr
electrophile
c) Nucleophilic Substitution
Typical reaction of saturated organic compounds
bearing polar bond as functional group, such as
haloalkane with alcohol.
Example :
Δ
CH3CH2Br + OH-(aq) CH3CH2OH + Br-(aq)
nucleophile
•
III) Elimination Reaction
An atoms or groups are removed from adjacent
carbon atoms of a molecule to form a multiple
bond (double or triple bond).
• Results in the formation of unsaturated molecules.
• Example :
Example : H
tautomerisme
H C C R H C C R
H OH H O
Exercises
Hydrocarbon
are compounds which
contain only carbon and
hydrogen atoms.
HIDROCARBONS
AROMATIC
ALIPHATIC
(contain one or more benzene ring)
ALKANES ALKENES
(saturated) (unsaturated) ALKYNES
contain only contain (unsaturated)
single bond C=C contain
C≡C
isobutane
CH3(CH2)2CH3 CH3CH(CH3)2
C5H12
IUPAC NOMENCLATURE
CH3CH2CH2CH2CHCH3
|
CH3
CH2
CH3
CH3CH2CH2CH2CHCH3
CH3 substituent
7 6 5 4 3
CH3CH2CH2CH2CH CH3 substituent
|
2 CH2
|
1 CH3
Use rule number 2 to locate the position
of the substituent.
CH3CH2CH2CH2CHCH3
Substituent
CH3 -methyl at C-2
2-methylhexane
Substituent
7 6 5 4 3 -methyl at C-3
CH3CH2CH2CH2CH CH3
|
2 CH
2
|
1 CH
3
3-methylheptane
Some Common Substituent Groups
Alkane name substituent
CH3
sec-butyl CHCH2CH3
CH3
tert-butyl CH3
CCH3
CH3
neopentyl 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
If two or more substituents are present, give
each substituent a number corresponding
to its location on the longest chain.
4-ethyl-2-methylhexane
If two substituents are present on the
same carbon atom, use that number twice
Example:
CH3
|3 4 5 6
CH3CH2CCH2CH2CH3
|
2 CH
2
|
1 CH
3
3-ethyl-3-methylhexane
If two or more identical substituents are
present, use prefixes di-(2 identical
substituents),tri-(3 identical substituents),
tetra-(4 identical substituents).
Commas are used to separate numbers
from each other.
Example:
CH3CH―CH CH3 2,3-dimethylbutane
| |
CH3 CH3
If there are two chains of equal length as
the parent chain, choose the chain with
the greater number of substituents.
7 6 5 4 3 2 1
4 3 2 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)
If branching occurs at an equal distance from
either end of the longest chain, choose the
name that gives the lower number at the first
point of difference.
6 5 4 3 2 1
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.
General formula:
CnH2n where n = 3, 4, 5, ……
NOMENCLATURE OF
CYCLOALKANES
C3H6 cyclopropane
C4H8 cyclobutane
C5H10 cyclopentane
If only one substituent is present, it is not
necessary to designate its position.
Examples:
Chlorocyclopropane
Cl
CH3 Methylcyclohexane
If two substituents are present, number carbon
in the ring beginning with the substituent
according to the alphabetical order
and
number in the direction that gives the next
substituent the lowest number possible.
Examples:
CH3
3
2
4 CH2CH3
1
5 6
1-ethyl-2-methylcyclohexane
NOT
1-ethyl-6-methylcyclohexane
2
Cl 3 1
Cl
4 5
1,3-dichlorocyclopentane
(NOT 1,5-dichlorocyclopentane)
When three or more substituents are
present, begin at the carbon with
substituent that leads to the lowest set of
locants.
Locants
Example:
CH2CH3 chloro 1 4
2 3
1
3 2
4 ethyl 3 2
Cl 4 1 CH3
methyl 4 1
5 6
6 5
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)
When a single ring system is attached
to a single chain with a greater number
of carbon atoms
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
1 3
1,3-dicyclohexylpropane
Examples:
CH2CH2CH2CH2CH3
1-cyclobutylpentane
Physical properties of alkanes & cycloalkanes
Physical Boiling
state Point
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 ↑
C-H is non polar bond
Intermolecular forces exist – London
dispersion
The London dispersion forces increase :
As molecular weight increases,
Molecular size increases
Molecular surface area increase
Mr ↑ boiling point ↑
Chain branching :
makes a molecule more compact
CH3CH2CH2CH3 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
Combustion
Halogenation
Combustion of alkanes
Alkanes burnt in air ( oxygen ) to give carbon
dioxide gas, water and heat.
y y
CxHy+ x O2 → x CO2 + H2O
4 2
+ Heat
Examples:
Combustion of alkane in excess oxygen
R–H + X2 hv R–X + HX
With methane, the reaction produces a mixture of
halomethane and a hydrogen halide.
Examples:
hv CH3Cl + CH2Cl2
i. CH4 + Cl2
+ CHCl3 + CCl4
+ HCl
hv
ii. CH3CH3 + Cl2 CH3CH2Cl + HCl
CH3 CH3
| |
hv CH CCH Cl + HCl
3 2
iii. CH3 CCH3 + Cl2
| |
CH3 CH3
(ii) & (iii): 1 product only because all the
hydrogen atoms are identical
CH3CH2CH2Br
hv
iv. CH3CH2CH3 + Br2 ( minor)
+ CH3CHCH3
|
Br
( major)
+ HBr
Reaction mechanism
hv
Cl – Cl 2Cl•
ii. Chain propagation steps
H
H-C H + •Cl •CH3 + HCl
H
3HC• + Cl Cl_ CH3Cl + Cl•
iii. Chain termination step.
H H Br
Increasing % yield
Exercise
Chlorination reaction of certain alkanes can be
used for laboratory preparations, for example in
the preparation of chlorocyclopentane from
cyclopentane. Give the mechanism for the
reaction.
12.2 ALKENES
General formula CnH2n , n 2.
Unsaturated hydrocarbon
CH3
H3 C C CH CH3
1 2 3 4
2-methyl-2-butene
(not 3-methyl-2-butene)
1 2 3 4 5 6
H3C C CH CH2 CH CH3
CH3 CH3
2,5-dimethyl-2-hexene
(not 2,5-dimethyl-4-hexene)
Step 4
1 2 3 4 5 6 7
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 3
1-methylcyclopentene
(not 2-methylcyclopentene)
1
6 2
5 3
CH3 CH3
4
3,5-dimethylcyclohexene
(not 4,6-dimethylcyclohexene)
MORE
Step 6
RCH=CHR RCH=CH-
-H
alkene alkenyl
CH2=CH- CH2=CHCH2-
vinyl group allyl group
Step 7
cis / trans
Cl Cl Cl H
C C C C
H H H Cl
cis-1,2-dichloroethene trans-1,2-dichloroethene
Give IUPAC names for the following alkenes
1)
2) CH3
CH3
3)
4) CH2CH3
CH3
5) CH3CH=CHCH2C(CH3)2CH3
Preparation of alkenes
a) Dehydration of alcohols
b) Dehydrohalogenation of alkyl halide
Dehydration of alcohols
Alcohols react with strong acids in the
presence of heat to form alkenes and water.
H2SO4 (conc.)
C C
C C + H2 O
H OH
Concentrated sulphuric acid (H2SO4) or
phosphoric acid (H3PO4) : as acidic catalysts
and dehydrating agents.
H2SO4 (conc.)
(2) H3C CH CH3 H2C CH CH3
OH + H2O
Mechanism for the
dehydration of alcohol
H3C CH CH2CH3 H SO (conc.) CH 3 CH=CHCH 3
2 4
OH (major product)
+ CH 2 =CHCH 2 CH 3
(minor product)
+ H 2O
Step 1:
Protonation of alcohol.
H H
H3C C CH2CH3 + +
:O H
:OH H
..
H H
H3C C CH 2 CH 3 + :O H
+ ..
: OH
H
Step 2:
Formation of carbocation
H H
H 3 C C CH 2 CH 3 +
H3 C C CH2 CH3
+:OH
carbocation
H
H
+ :O H
..
Step 3:
Formation of alkenes
H H H H
+
H C C C CH3 :O H
b + ..
H H
a
Root a : major product
Root b : minor product
H H H
C C + +
: O H
H3C CH 3 H
stable alkenes
+ CH 2 =CHCH 2 CH 3
(minor product)
Rearrangement During Dehydration
of Alcohol
Example 1:
CH3 H
H2 SO4 (conc.)
H3C C C CH3
CH3OH
CH3
H 3C C C CH3
CH3
(major product)
CH
3
+ H C C CH CH
2 3
CH
3
(minor product)
Step 1 and Step 2 are similar to
the previous example.
Step 3:
Now the rearrangement occurs.
+ +
H C C C CH H C C C CH
3 3 3 3
CH H rearrangement CH H
3 3
2o carbocation 3o carbocation
(less stable) (more stable)
The rearrangement occurs through the
migration of an alkyl group (methyl) from
the carbon atom adjacent to the one with the
positive charge.
CH
3
(b) HC C C CH
3 3
CH
3
(b) (major product)
more stable alkene
The
The final
final step
step can
can occur
occur in
in two
two ways:
ways:
CH H CH
3 H2SO4 (conc) 3
H C C C CH H C C CH CH
3 3 3 3
H OH (major product)
CH
3
+ H C C CH CH
2 2 3
(minor product)
(2) Dehydrohalogenation of Alkyl Halides
The elimination of a hydrogen and a halogen
from an alkyl halide to form an alkene.
alcohol
C C + KOH
reflux
C C
H X
+ HX
Saytzeff’s rule is used to determine the major
product
Examples:
(1)
Cl
alcohol
H3C CH CH2CH2CH3 + KOH
reflux
CH2
+
CH3
(major product)
(4)
CH3 H
CH3 C C CH3 + KOH alcohol
CH3 Cl reflux
CH3 H CH3
CH2 C C CH3 CH3 C C CH3
CH3 CH3
2,3-dimethyl-1-butene 2,3-dimethyl-2-butene
(minor product) ( major product)
2 alkyl groups 4 alkyl groups
Chemical Reaction of Alkenes
Comparison of The Reactivity Between
Alkanes and Alkenes
Alkenes are more reactive compared to alkanes.
Alkanes have carbon-carbon single bonds (σ bonds)
while alkenes have carbon-carbon double bonds (π
bonds).
The double bond is a site of high electron density
(nucleophilic).
Therefore most alkenes reactions are electrophilic
additions.
Electrophilic Additions
Mechanism
H H H
slow +
C C + X Y H C C H
H H X H
-
+ Y
H H H
+ - fast
H C C H + Y H C C H
X H X Y
Example:
i.
H3C CH3
slow
C C + H Cl
H3C CH3
CH3CH3
+
H3C C C CH3 + -
Cl
H
CH3CH3
fast
H3C C C CH3 + Cl-
+
H
CH3CH3
H3C C C CH3
H Cl
Addition Reaction of Alkenes
(1) Hydrogenation
The reaction of an alkene with hydrogen in the
presence of catalyst such as platinum, nickel and
palladium to form alkane.
Pt or Ni or Pd
C C + H2 C C
H H
Examples:
(1)
Pt /Ni / Pd
H3C C CH2 + H2 H3C CH CH3
CH3 CH3
Pt /Ni / Pd
(2) + H2
(2) Halogenation of Alkenes
CH2Cl2
C C + X2 C C
X X
Example:
CH3
CH2Cl2
H3C C C CH3 + Cl 2
H
Cl Cl
H3C C C CH3
CH3H
When bromine is used for this reaction, it can
serve as a test for the presence of carbon-carbon
double bonds.
C C
Br Br
Observation: The reddish brown bromine decolourised
(3) Hydrohalogenation : Markovnikov’s rule
Hydrogen halides (HI, HBr, HCl and HF) add to the
double bond of alkenes to form haloalkanes.
C C + HX C C
H X
The addition of HX to an unsymmetrical alkenes,
follows Markovnikov’s rule.
Markovnikov’s Rule:
CH 3
+
slow
CH 3 H Br
C CH CH 3
CH3
CH3 C CH CH3 + Br -
+
30 Carbocation
CH3
-
fast
CH3 C CH CH3 + Br
+
CH3
CH3 C CH CH3
Br H
(4) Addition of HBr to Alkenes in The
Presence of Peroxides
(Anti Markovnikov’s rule)
When alkenes are treated with HBr in the presence
of peroxides, ROOR (eg: H2O2) the addition
occurs in an anti-Markovnikov manner
ROOR
H2C CH CH3 + HBr
Br CH2CH2CH3
Complete the following reactions:
(1)
H2 O 2
H3C CH2C CH2 + HBr
CH3
(2)
CH2 H2 O2
+ HBr
(ii) In aqueous (Halohydrin Formation)
C C + X2 + H2O C C
X OH
X2 = Cl or Br halohydrin
Example:
H H H H
C C + Br2 + H2O H C C H
H H Br OH
2-bromobutanol
Unsaturated test
Observation : the reddish brown bromine decolourised
If the alkenes is unsymmetrical, the halogen
ends up on the carbon atom with the greater
number of hydrogen atoms.
Example:
H 3C C CH2 + Br 2 + H2O
CH3
CH3H
H3 C C C H
OH Br
1-bromo-2-methyl-2-propane
Complete the following reaction:
+ Br2 + H2O
CH3
(5) Hydration of Alkene
The acid-catalyzed addition of water to the
double bond of an alkene (hydration of an
alkene) is a method for the preparation of low
molecular weight alcohols.
+
H3O
C C + H2O C C
H OH
Example:
+
H3 O
H3C C CH2 + H2O
CH3
OH
H3C C CH3
CH3
Complete the following reactions:
(1)
+
CH2 H3 O
+ H2 O
(2)
+
H3O
H2C CH CH3 + H2O
Mechanism
STEP 1
CH3 H
..
CH3 C CH CH3 + H O+ H
CH3
CH3 C CH CH3
+
H
STEP 2
CH3
..
+ ..
H
CH3
CH3 C CH CH3
H O+ H
..
H
STEP 3
CH3
CH3 C CH CH3
H O+ H
..
CH3
..
OH H
(6) Addition of Sulphuric Acid to
Alkenes
Alkenes dissolve in concentrated sulphuric acid
to form alkyl hydrogen sulphates.
Alkyl hydrogen sulphates can be easily
hydrolysed to alcohols by heating them with
water.
The overall result of the addition of sulphuric
acid to alkenes followed by hydrolysis is the
Markovnikov addition of -H and -OH.
CH3CH3
H3 C CH3
conc. H2 SO 4 H3 C C C CH3
C C
H3 C CH3 H OSO 3 H
alkyl hydrogen sulphate
CH3CH3
H2O H3 C C C CH3
heat
H OH
Example:
OSO3H
conc.H2SO4
H2C CH CH 3 H3C CH CH2
H
OH
H2O
H3 C CH CH2
heat
H
7 ) Oxidation of Alkenes
Alkenes undergo a number of reactions in
which the C=C is oxidized
KMnO4 ozonolysis
basic,cold,dilute
acidic,hot,concentrated
i) With cold and dilute potassium
permanganate, KMnO4
C C + MnO2
OH OH (brown precipitate)
-
OH ,H2 O
H2C CH2 + KMnO4
cold
H H
H C C H + MnO2
OH OH
ii) With hot potassium permanganate
solutions to alkenes
CH3 -
(i) OH ,heat
H3C C C CH3 + KMnO4
(ii) H3O
+
CH3
O O
H3C
C
CH3
+ H3C
C
CH3
If a hydrogen is present at double bond, one
of the carbonyl-containing products is a
carboxylic acid;
HO
C
CH3
+ CO2 + H2 O
The oxidative cleavage of alkenes can be
used to establish the location of the double
bond in an unknown alkene.
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?
(i) OH-,heat
C7 H14 + KMnO4
(ii) H3 O
+
O O
H3C
CH2
C
OH
+ H3C
CH2 C
CH2 OH
Answer:
O O
H3C C CH2 C
CH2 OH H3C CH2 OH
propanoic acid butanoic acid
H H
H3C CH2C C CH2CH2CH3
3-heptene
Example
An unknown alkene undergoes oxidation in hot
basic KMnO4 followed by acidific to give the
following product:
O O
CH3CCH2CH2CH2CH2C OH
O O
ozonide
Ozonides:
very unstable compounds
R
O O
ozonide
H
C=O + O=C
R
Example:
CH3 (i) O3
+
H3C C CH CH3 (ii) Zn,H2O/H
CH3 CH3
H3C
C
O
+ H
C
O
Exercise
1. Write the structure of alkene that would
produce the following products when
treated with ozone followed by water, zinc
and acid
CH3COCH3 and CH3CH(CH3)CHO
Example
Deduce the structural formula of an alkene
that gives the following compound when it
reacts with ozone in the presence of Zn / H+.
O=CH-CH2-CH2-CH(CH3)CH=O
2. Acid-catalyzed dehydration of neopentyl
alcohol, (CH3)3CCH2OH, yields 2-methyl-
2-butene as the major product. Outline a
mechanism showing all steps in its
formation.
Exercise
Compounds A, B, C and D are isomers with the
molecular formula C4H8. A and B give a positive
Baeyer test, while C and D do not. A exists as
cis- and trans- isomers, while B does not have
geometrical isomers. C has only secondary
hydrogen, while D has primary, secondary and
tertiary hydrogen. Give the IUPAC names for A,
B, C, and D.
The origin of August Kekulé’s view of benzene structure:
August Kekulé
“In variably, my device works
as I imagined it should.
In twenty years there has not been
single exception.”
NIKOLA TESLA
“Imagination is more important
than knowledge.”
ALBERT EINSTEIN
AROMATIC COMPOUNDS
Introduction to
14.1
aromatic Compounds
Friedel-Craft acylation
electrophilic substitution
oxidation of
activating and alkylbenzene
deactivating group
substitution of
ortho-para and meta director toluene
DISCOVERY OF BENZENE
Empirical formula = CH
named “benzin”
H C C H
C
or
C C
H C H
H
equivalent to
resonance hybrid
Cyclic Planar
Conta
in par
numb ticula
e r of r
pl e t e ly electr ∏
Com ted on
nju g a obe
co ys HÜ
Rule ckel’s
THE CRITERIA FOR AROMATICITY
HÜckel’s Rule
* cyclic, planar and completely
conjugated compounds that
contain [4n+2] ∏ electron
(n=0,1,2…..) are said to be
aromatic
Erich HÜckel
(1896-1980)
Benzene
aromatic
Benzene is aromatic because:
contains 6∏ electrons
(obeys HÜckels Rule)
[4n+2] ∏ = [4(1) + 2]∏
cyclic, planar and has double
= 6 ∏ electrons bond in the ring
THE CRITERIA FOR AROMATICITY
EXAMPLE
Aromatic
naphthalene
4n+2= 4(2)+ 2
10 ∏ electrons
Nomenclature of benzene
14.2
and its derivatives
EXAMPLE:
CH3
Common: toluene
IUPAC: methylbenzene
MONO SUBSTITUTED BENZENE
Benzene is the parent name and the substituent
is indicated by a prefix.
F Cl Br
NO2 CH2CH3
nitrobenzene ethylbenzene
IUPAC rules allow some common names
to be retained.
CH3 OH NH2
COOH CHO
1,2–dinitrobenzene 1,3–dinitrobenzene
or or
o–dinitrobenzene m–dinitrobenzene
NO2
1
2
3
4
NO2
1,4–dinitrobenzene
or
p–dinitrobenzene
DISUBSTITUTED BENZENE
Two Different Substituents
Cl
Br
1 2 Br Br
3 I
4
2–bromo–1–chloro–3–iodobenzene
Br
1,2,4–tribromobenzene
C atom bearing the subtituent that define the
new parent name is numbered as C1.
OH
COOH
1
2 NO2 1
6 2
3 5 3
4 OH
HO 4
NO2
3,5–dihydroxybenzoic acid
2,4–dinitrophenol
3
Br 4 2 CH3
1 CH3
4–bromo–1,2–dimethylbenzene
3
Br 4 2 CH3
1 CH3
4–bromo–1,2–dimethylbenzene correct
4–bromo–o–dimethylbenzene
1 CH2
3 4 5 6 7
2 CH–CH
2–CH2–CH2–CH2–CH3
2–phenylheptane
Phenyl = C6H5– = Ph
14.2-12
1 2 3 4 2 1
CH2–C C–CH3 CH2–CH2–OH
1–phenyl–2–butene 2–phenylethanol
14.2-13
BENZYL GROUP
CH2—
CH2Br CH2OH
Br2 / CCl4
no addition of Br2
(no decolorization)
Br
FeBr3
+ Br2
benzene bromobenzene
H E
+ E+ + H+
electrophile
14.3-05
X2, FeX3 X
(X = Cl Br) + HX halogenation
HONO2
NO2
+ H2O nitration
H2SO4
O
O
RCCl , AlCl3
C–R Friedel-Crafts
+ HCl Acylation
14.3-07
GENERAL MECHANISM
H H
H
H H H
E E E
H H H
+ H H H
+ +
H H H H H H
H H arenium ion H
14.3-08
ARENIUM ION
+
E+ E
H
H H H H
H H
+
E+ E – H+
H E
STEP 2 E
E
H + H+
+
14.3-11
HALOGENATION
Reactants: benzene and halogens (Cl2 or Br2).
Conditions:
Lewis acid such as FeCl3 and FeBr3
+ Br2 no reaction
(decolorization not observed)
Br
FeBr3
+ Br2 + HBr
bromobenzene
14.2-13
MECHANISM
STEP 1 Formation of Br+
+ –
Br–Br + FeBr3 Br—Br–FeBr3 Br+ + FeBr4–
complex
STEP 3 Loss of H+
Br FeBr4– Br
H + HBr + FeBr3
+
14.3-14
FUNCTION OF LEWIS ACIDS
HNO3 NO2
H2SO4
nitrobenzene
+ H+ + HSO4–
12.5-49
MECHANISM
H2O + NO2+
nitronium ion
STEP 2 Formation of arenium ion
NO2
H
+ NO2+ +
STEP 3 Loss of H+
NO2 HSO4–
NO2
H + H2SO4
+
12.5-51
FRIEDEL–CRAFT ALKYLATION
Reactants: benzene and haloalkane.
Conditions:
Catalyst: Lewis acid such as AlCl3.
R
AlCl3
+ R–X + HCl
alkylbenzene
Alkylation = transfer an
alkyl group to benzene
12.5-52
12.5-53
EXAMPLE:
Cl
CH(CH3)2
AlCl3
+ CH3CHCH3 + HCl
2–chloropropane
isopropylbenzene
C(CH3)3
AlCl3
+ (CH3)3C–Cl + HCl
2–chloro–2–methylpropane
tert–butylbenzene
12.5-54
MECHANISM
STEP 1 Formation of carbocation
+ -
: :
: :
(CH3)2CHCl: + AlCl3 (CH3)2CH–Cl–AlCl3
(CH3)2CH+ + AlCl4–
carbocation
STEP 2 Formation of arenium ion
CH(CH3)2
+CH(CH ) H
+ 3 2 +
STEP 3 Loss of H+
AlCl4–
CH(CH3)2
CH(CH3)2
H
+ + HCl
OTHER FACTS ABOUT 12.5-55
FRIEDEL–CRAFT ALKYLATION
Rearrangement can occur, especially when
1o haloalkanes are used.
CH2CH2CH2CH3
EXAMPLE:
35%
CH3CH2CH2CH2Cl butylbenzene
CH3
AlCl3 +
CHCH2CH3
65%
Rearrangement: sec–butylbenzene
H
+ +
CH3—CH2—CH—CH2 CH3—CH2—CH—CH3
1o carbocation 2o carbocation
12.5-56
FRIEDEL–CRAFT ACYLATION
Reactants: benzene and acid chloride.
Product: ketone.
Conditions:
Catalyst: Lewis acid such as AlCl3.
EXAMPLE:
O
O
AlCl3 CCH3
+ CH3C—Cl + HCl
acetyl chloride
acetophenone
12.5-57
ACYL GROUP
O
RC—
acyl group
EXAMPLE:
O
O
–C—
CH3C—
acetyl group benzoyl group
Acylation = transfer an
acyl group to benzene
12.5-59
MECHANISM
STEP 1 Formation of acylium ion
:O: :O:
R–C–Cl + AlCl3 R–C–Cl–AlCl3
: :
R–C+═O R–C≡O+ + AlCl4–
acylium ion
Formation of arenium ion R
STEP 2
C=O
+ R–C+═O H
+
STEP 3 Loss of H+
R AlCl4– R
C=O
C═O
H
+ + HCl
12.5-61
SUBSTITUENT EFFECT
EXAMPLE:
NO2 Cl H OH
relative rate
6 x 10–8 0.033 1 1000
of nitration
reactivity
12.5-63
EFFECT ON ORIENTATION
Ortho–para directors
Tend to direct the incoming group into
ortho and para positions.
Meta directors
Tend to direct the incoming group into
meta position.
EXAMPLE: ortho-para director
CH3 CH3 CH3 CH3
HNO3 NO2
+ +
H2SO4 NO2
(59%) (37%) NO2 (4%)
12.5-64
CLASSIFICATION OF SUBSTITUENTS
DIRECTING ACTIVATORS
Increasing activation
●● ●● ●●
—NH2 —NHR —NR2
●●
—OH
●●
●● General structure:
—OR
●● —R or —Z● ●
●●
—NHCOR
Alkyl groups or have
nonbonded electron pair
—R on the atom bonded to
benzene ring
12.5-66
EXAMPLE:
DIRECTING DEACTIVATORS
●● ●●
—F ●
● —Cl●
●
●● ●●
●● ●●
—Br●● — I●
●
●● ●●
General structure
●●
—X●● (halogens)
●●
12.5-68
EXAMPLE:
Cl Cl Cl
NO2
HNO3
+
H2SO4
chlorobenzene (35%) (64%) NO2
12.5-69
META– DIRECTING ACTIVATORS
—CHO
—COR
—COOR General structure:
—Y (+ or –)
—COOH
—CN
Have a full or partial
—SO3H positive charge on the
atom bonded to
—NO2 benzene ring
+
—NR3
Increasing deactivation
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 CH3
Cl— CH3—
electron–withdrawing electron–donating
12.5-71
Activating Groups
CH3
Release electrons to the ring NO2
Deactivating Groups
Cl
Withdraw electrons from the ring NO2
CF3 CH3
NO2 NO2
NO2
+ +
+
benzylic H
CH3
CH3 CH(CH3)2
EXAMPLE: 12.5-76
CH3 COOH
KMnO4
heat
toluene benzoic acid
Na2Cr2O7
O2N CH3 O2N COOH
heat
p–nitrotoluene p–nitrobenzoic acid
KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
isopropyl toluene terepththalic acid
12.5-77
KMnO4
CH3 CH(CH3)2 HOOC COOH
heat
KMnO4
CH3 C(CH3)3 HOOC C(CH3)3
heat
12.5-78
HALOGENATION OF TOLUENE
EXAMPLE: (dichloromethyl)benzene
CH3 CH2Cl CHCl2 CCl3
Cl2 Cl2 Cl2
heat or heat or heat or
light light light
CH3
CH3
CH3
Br2 Br2 +
FeBr3
toluene Br2
●
CH2 12.5-79
benzylic
radical
benzene toluene
benzo[a]pyrene
HALOALKANES
FJ / Chemistry Unit, KMPk / Mac 2006 1
15.1 : Introduction
Haloalkanes or alkyl halides
- compounds that contains halogen atom bonded
to an sp3 hybridized carbon atom.
methyl halide
CH 3 X - halogen is bonded to
methyl group
Primary (10) halide
R CH 2 X - halogen is bonded to 10
carbon atom
Secondary (20) halide
R
- halogen is bonded to 20
R CH X carbon atom 3
General Formula Classification
X Aryl halide
- halogen is bonded to aromatic
ring
CH 2 X
** Not a aryl halide
4
Example :
Classify the following haloalkanes :
i. CH 3 CH 2 Br 10
ii. CH 3 CH (Cl)CH 3 20
H3C Cl
iv. 30
5
15.1.2 : IUPAC Nomenclature
6
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 8
Example :
v. Br
4-bromocyclohexene
vi. CH 2 Cl vii. CH 3
Cl
(chloromethyl)benzene 2-chlorotoluene
9
15.1.3 : Structure of Haloalkane
The carbon – halogen bond in haloalkene is polar
because halogens is more electronegative than carbon.
δ+ δ- electrophilic
C X
site
General reaction :
_ _ _
R X + N u: R _N u + X:
11
(a) : Hydrolysis of Haloalkane with Aqueous Solution
of NaOH (H2O/NaOH)
H2 O
R_ X + NaOH R_ OH + NaX
Example :
CH3 CH3
_ _ H2 O
CH3 C Br + NaOH CH3 _ C _OH + NaBr
CH3 CH3
12
(b) : Reaction of Haloalkane with Potassium Cyanide
(KCN)
_ _ alcohol _
R X + CN R_ CN + X
reflux
Example :
NH 3 _ NH 3 _
R_ X +
RNH 3 X _ +
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
15
(A) : Unimolecular Nucleophilic Substitution Reaction
(SN1)
rate = k [R3C-X]
17
The mechanism of SN1 reaction involves 2 steps.
R R
_ _ fas t
R C + + N u: R_ C _ N u
R R 18
Example 1 :
Reaction of 2-bromo-2-methylpropane with H2O.
CH 3 CH 3
CH 3 _ C _ Br + H 2 O CH 3 _ C _ OH + HBr
CH 3 CH 3
SN1 mechanism :
CH 3 CH 3
s low _
CH 3 _ C _ Br CH 3 _ C + + Br
CH 3 CH 3 19
Step 2 : Nucleophilic attack on the carbocation
CH 3 CH 3
fa s t H
CH 3 _ C + + H2O _ _
CH 3 C O
+ H
CH 3 CH 3
CH 3 CH 3
H
_ _
CH 3 C O + H2O CH 3 _ C _ OH + H 3 O +
+ H
CH 3 CH 3
20
Example 2 :
Write the mechanism for the following reaction.
CH3 CH3
CH3 _C _CH2Br + NaOH(aq) CH3 _ C _CH2CH3 + NaBr
CH3 OH
SN1 Mechanism :
CH 3 CH 3
_
CH 3 _ C _ CH 2 _Br s low _ _
CH 3 C CH 2 + Br
+
CH 3 CH 3 21
Rearrangement :
CH 3 CH 3
CH 3 _ C _ CH 2 1,2-meth yl s hift CH 3 _ C _ CH 2
+ +
CH 3 CH 3
CH 3 CH 3
_
CH 3 _ C _ CH2 + OH fas t CH 3 _ C _ CH 2 CH 3
+
CH 3 OH
22
Exercise 1 : (Feb 2003)
i. KCN
ii. NaOH/H2O
iii. excess NH3
23
Exercise 2 : (Mac 2002)
CH3
CH3 C Br
CH3
Steric effect
- is an effect on relative rates caused by the space-
filling properties of those parts of a molecule
attached at or near to the reacting site.
25
The reactivity on SN2 reaction depends on the size of
atoms or groups attached to a C – X.
increasing reactivity
26
The rate of reaction depends on the concentration of
the haloalkane and the concentration of nucleophile.
General Mechanism :
R R R
slow fast Nu C
C X Nu C X + X-
Nu:- H H
H H H H
27
transition state
In SN2 reaction, the nucleophile attacks from the back
side of the electrophilic carbon, that is, from the side
directly opposite bonded to the halogen.
28
Example 3 :
Reaction of ethyl bromide with aqueous sodium
hydroxide.
SN2 Mechanism :
SN1 SN2
General reaction :
H
_C_C_ _ _ _
+ :B C C + X
X
alkene
haloalkane base
31
Example :
Br
CH 3 CH 2 ON a
i. CH 3 CHCHCH 3 CH 3 C CHCH 3
CH 3 CH 2 OH
CH 3 CH 3
major
+
CH 3 CHC CH 2
CH 3
minor
ii.
Br CH 3 CH 2 ON a CH 3 CH 2
CH 3 CH 3 CH 2 OH +
major minor 32
15.2.4 : Synthesis of Organomagnesium
Compound ( Grignard Reagent )
ii.
ether
Cl + Mg MgCl
33
15.2.4.1 : Synthesis of Alkanes, Alcohols and
Carboxylic Acids from Grignard
Reagents.
The Grignard reagents undergo many reactions that
make them useful as a starting materials in the
synthesis of other organic compounds.
H+
RMgX + H 2 O 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.
H 2 O/H +
CH 2 MgCl CH 3
+ Mg(OH)Cl
35
(ii). Synthesis of 1o alcohol
O H
R-MgX + H-C-H R-C-OMgX
H
H 2 O,H +
H
R-C-OH + Mg(OH)X
36
H
Example :
i.
O H
H 3 O+
CH 3 MgBr + H-C-H CH 3 -C-OH + Mg(OH)Br
H
ii.
MgBr O CH 2 OH
H 3 O+
+ H -C-H + Mg(OH)Br
37
(iii). Synthesis of 2o alcohol
H 2 O,H +
R'
R-C-OH + Mg(OH)X
H 38
Example :
O
i. CH 3 CH 2 MgBr + CH 3 CH 2 -C-H
H 2 O/H +
H
CH 3 CH 2 -C-CH 2 CH 3 + Mg(OH)Br
OH
ii.
CH 3
O
MgCl H 2 O/H + C-OH
+ CH 3- C-H + Mg(OH )Cl
H
39
(iv). Synthesis of 3o alcohol
O R'
R-MgX + R'-C-R" R-C-OMgX
R"
H 2 O,H +
R'
R-C-OH + Mg(OH)X
40
R"
Example :
i. O
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.
CH 3
O
MgCl
H 3 O+ C-OH
+ CH 3- C-CH 3 + Mg(OH )Cl
CH 3 41
(v). Synthesis of carboxylic acid
O
RMgX + O C O R-C-O-MgX
O O
H+
R-C-O-MgX + H 2 O R-C-OH + Mg(OH)X
42
Example :
O
CH 3 CH 2Mg I + CO 2 CH 3 CH 2- C-O-MgI
O O
H+
CH 3 CH 2- C-O-MgI + H 2 O CH 3 CH 2 COH + Mg(OH)I
43
15.2.5 : Wurtz Reaction
dry ether
2RX + 2Na RR + 2NaX
Example:
Example:
45
15.2.6 : Importance of Haloalkanes as Inert
Substance
Haloalkanes Uses
Click me
for intro!
1
INTRODUCTION
Alkane with hydroxyl group (–OH)
General formula for aliphatic alcohol,
CnH2n+1OH
Aromatic alcohol – phenol (-OH attached
to the benzene rings)
2
INTRODUCTION
OH CH2-OH
CH3CH2-OH
3
INTRODUCTION
OH OH OH
CH3
Br
4
CLASSIFICATION
Methyl alcohol CH3-OH
10 Alcohols R-CH2-OH
R
20 Alcohols R-CH-OH
R
30 Alcohols 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 cyclohexanol
alcohol
6
Naming the alcohol
1. The suffix ‘–e’ in the alkane parent name is
replaced by ‘–ol’
2. The location of the –OH on the longest chain
is given by the smallest possible number
7
IUPAC rules for naming alcohols
1. Determine parent name
2. Give the lowest number to the carbon
bearing the –OH group
3. Identify substituent groups and their position
4. Name the alcohol
8
Naming Alcohols, R-O-H:
CH3 CH3
CH3CHCH2CHCH3 CH3CCH2CH2CH3
OH OH
4-methyl-2-pentanol
2-methyl-2-pentanol
2o 3o
CH3
HO-CHCH2CH3 CH3CH2CH2-OH
10
For phenol, C attach to the –OH group is C 1
OH OH OH
CH3
CH2CH3 Br
11
Alcohol with 2 hydroxy groups
Structure General name IUPAC name
CH2(OH)CH2-OH
ethylene glycol 1,2-ethanediol
CH3CH(OH)CH2-OH
propylene glycol 1,2-propanediol
HO-CH2CH2CH2-OH trimethylene 1,3-propanediol
glycol
OH-CH2CHCH2-OH
OH
glycerol 1,2,3-propanetriol
12
Benzene derivatives with 2 –OH groups are
name as benzenediol
OH OH OH
OH
OH
OH
13
EXCERCISE
(a)
-CH2CH(CH3)CH2-OH
(b)
-OH
NO2
(b)
-OH
Br
14
PHYSICAL PROPERTIES
Most simple alcohols are liquids
MeOH & EtOH are volatile liquids, b.p.
65oC & 78oC respectively
Mr , b.p.
ROH with C > 12 are solids
15
PHYSICAL PROPERTIES
16
PHYSICAL PROPERTIES
(ii) Boiling point
As molecular weight increase, van der Waals
forces increase, boiling point will increase too.
18
PHYSICAL PROPERTIES (Solubility)
δ+
H
δ-
R O
Hydrophilic area
δ- H Hydrogen
O δ+ bonding
H
R OH
H
δ- δ+
R O Hydrophobic area
H
O δ+
H
δ-
19
PHYSICAL PROPERTIES (Solubility)
Phenol is not completely soluble in water below
66oC, but completely soluble above this temp.
Phenol is a colourless crystalline solid which is
hygroscopic
4-nitrophenol is more soluble in water than 2-
nitrophenol because can form H-bonding with
water molecules
20
PHYSICAL PROPERTIES (Solubility)
2-nitrophenol 4-nitrophenol
δ-
δ- O
δ+ O δ+ O H H
H δ- δ+
N
O
δ- O
N
δ+
O
O δ+ δ-
δ- H O
Intramolecular H-bonding δ+
H H
Intermolecular H-bonding
21
Acidity of phenol & alcohol
22
Acidity of phenol & alcohol
CH3CH2O- is e- richer than OH-, thus
H2O > acidic than CH3CH2OH
Phenol > acidic than H2O & CH3CH2OH
because phenoxide ion formed is more
stable
The phenoxide ion formed is stabilised
by resonance effect
23
Acidity of phenol & alcohol
O H O -
release proton
+ H+
Phenoxide ion
24
Phenoxide ion stability
O - O O O
- -
Oδ-
δ- δ-
δ-
25
Example:
OH CH2CH2-OH CH2-OH OH
acidity increase
26
Example:
COOH OH
Na2CO3 KOH K, Na
NaHCO3 NaOH NaH
Weak bases Strong bases Very strong bases
27
EXCERCISE
29
PREPARATION OF ALCOHOLS
2.Hydration of Alkenes
follows Markovnikov’s rule
Example:-
30
PREPARATION OF ALCOHOLS
Mechanism
CH3CH-CH3
●
● OH
●●
31
PREPARATION OF ALCOHOLS
3. Hydrolysis of Haloalkanes
CH2Cl CH2OH
+ NaOH(aq)
32
PREPARATION OF ALCOHOLS
4. Addition of Grignard reagent to
carbonyl compounds
33
PREPARATION OF ALCOHOLS
1o Alcohol CH3CH2CH2-OH
+ Mg(OH)Cl
34
PREPARATION OF ALCOHOLS
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 O-MgCl
CH3-MgCl + CH3-C-CH3 CH3-C-CH3
propanone CH3
H3O+
O-H
3o Alcohol CH3-C-CH3 + Mg(OH)Cl
CH3
36
EXCERCISE
CH3
ii.
H2O / H+
-CH=CH-CH3 B + C
37
ALCOHOL REACTIONS
(a) As an acid
38
ALCOHOL REACTIONS
(a) As a base
●● ●●
CH3CH2-O-H
●●
+ HA CH3CH2O+-H + A-
H
39
ALCOHOL REACTIONS
(1) Esterification
O O
H+,
R-C-OH + R’-OH R-C-OR’ + H-O-H
40
ALCOHOL REACTIONS
(1) Esterification
Example:-
O H+, O
CH3C-OH + CH3-OH CH3C-OCH3 + H-O-H
41
ALCOHOL REACTIONS
(1) Esterification
Alcohol reacts with acyl chloride to form ester
O O
base
CH3C-Cl + CH3-OH CH3C-OCH3 + HCl
42
ALCOHOL REACTIONS
(2) Dehydration of alcohol
•Involve formation of carbocation
•Possible of rearrangement
H2SO4(con.)
CH3CH2CH2OH CH3CH=CH2
1800C
propanol propene
43
ALCOHOL REACTIONS
(3) Formation of haloalkane
44
ALCOHOL REACTIONS
Example:-
• ROH + HX RX + H2O
45
ALCOHOL REACTIONS
(3) Formation of haloalkane
•ROH reacts with PX3, PX5 , SOCl2
General reaction:
(i) 3ROH + PX3 3RX + H3PO3
(ii) ROH + PCl5 RCl + POCl3 + HCl
(iii)ROH + SOCl2 RCl + SO2 + HCl
46
ALCOHOL REACTIONS
(4) Oxidation of alcohols
47
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
O O
[O] [O]
RCH2OH RC-H RC-OH
48
ALCOHOL REACTIONS
(4) Oxidation of 1o alcohol
Example:-
O O
K2Cr2O7 /H+ K2Cr2O7/H+
CH3CH2OH CH3C-H 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)
O
CH3CH2CH2OH + PCC CH3CH2C-H
propanol propanal
50
ALCOHOL REACTIONS
(4) Oxidation of 2o alcohol
• form ketone which cannot be oxidised further
under normal conditions
R R
[O]
R’CH-OH R’C=O + H2O
2o alcohol 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
[O]
R’-C-OH no reaction
R’’
3o alcohol
52
Chemical test for R-OH
Lucas test
• Lucas reagent : HCl(con.) + ZnCl2
• 3o R-OH + Lucas reagent – reacts
immediately to form cloudy haloalkane
• 2o R-OH + Lucas reagent –takes about 5-10
minutes
• 1o R-OH + Lucas reagent – no visible
changes unless heated
53
Example: OBSERVATIONS :
CH2OH
HCl / ZnCl2 Does not turn
cloudy
OH
HCl / ZnCl2 Turn cloudy
within 5 minute
54
OBSERVATIONS :
CH3
OH Turn cloudy
HCl / ZnCl2 immediately
55
Haloform Reaction
Methyl carbinol cleavage to give Carboxylic
acids and Haloform
H
X2 , H+
CH 3 C H HCX 3 + H C OH
OH-
OH O
H
X2 , H+
CH 3 C R HCX 3 + R C OH
OH-
OH O
56
IODOFORM TEST
OH
CH3CH2CCH3 + 3I2 base (OH-)
2-butanol
CH3CH2COO- + CHI3↓
yellow precipitate
(iodoform)
57
PHENOL
Manufacture of phenol by Cumene process
(a) Friedel-Crafts reaction
CH3-CH-CH3
AlCl3
+ CH3CH=CH2
Isopropylbenzene
(cumene)
58
PHENOL
(b) Oxidation of Cumene
O -OH
CH3-CH-CH3
CH3-C-CH3
1200C
+ O2 Cumene
hydroperoxide
59
Phenol reactions
1. Reaction at functional group -OH
(a) Reaction with Na
OH O-Na+
+ Na + ½ H2
60
Phenol reactions
1. Reaction at functional group -OH
(b) Reaction with NaOH
OH O-Na+
+ NaOH + H2O
61
Phenol reactions
2. Electrophilic substitution reactions
(a) Halogenation (Bromination)
-OH is ortho-para director
in Br2, aqueous solution, white precipitate 2,4,6-
tribromophenol 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 OH
Br
CS2
+ Br2 + + HBr
50C
Br
63
Phenol reactions
2. Electrophilic substitution reactions
(b) Nitration
OH OH
Dilute HNO3 NO2
+
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 + Cl-
65
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
67
EXERCISE 2
68
Common used of alcohol and
phenol
Ethyl alcohol is a poison. LD50 =
~10g/Kg orally in mice.- Nausea,
vomiting, flushing, mental excitement or
depression, drowsiness, impaired
perception, loss of coordination, stupor,
coma, death may occur. (intoxication)
Phenol is an important industrial
chemical. Major use is in phenolic resins
for adhesives and plastics.
69
Phenols in Medicine
Many phenols are used as antiseptics and
disinfectants.
OH OH OH
OH OH
CH2CH2CH2CH2CH2CH3
71
17.0 CARBONYL COMPOUNDS:
ALDEHYDES AND KETONES
17.1 Introduction
Aldehyde ketone
O O
R C H R C R
1
17.2 Nomenclature
2
Example
O
butanal
CH3CH2CH2C H
CH3 O
2-ethyl-4-methylpentanal CH3CH CH2CH C H
CH2 CH3
CH3 O
3,5-dimethyl-2-hexanone CH3CH CH2CH C CH3
CH3
3
IUPAC nomenclature and common names of some carbonyl
compounds.
i) 2- methylpentanal
O
CH3CH2CH2CH C H
CH3
ii) 3- hexanone
CH3CH2C CH2CH2CH3
5
iv) 3-ethylcyclopentanone
CH3 CH2 O
v) 3-cyclohexylpropanal
CH2 CH2 C H
O
6
17.3 Synthesis of Aldehydes and Ketones
a) Oxidation Alcohols
7
Example
1.
H O
PCC
CH3 C OH CH2Cl2
CH3 C H
H
ethanol ethanal
(alcohol 10) (aldehyde)
2.
CH3 O
KMnO4, H+
CH3 C OH CH3 C CH3
heat
H
2-propanol propanone
(alcohol 20)
8
3.
CH3
no reaction
CH3 C OH
CH3
2-methyl-2-propanol
(alcohol 30)
9
b) Ozonolysis of Alkenes
R R1 O O
i. O3
C C ii. H2O/Zn
R C H + R1 C H
H H
R R1 O O
i. O3
C C ii. H2O/Zn
R C R2 + R1 C R3
R2 R3
Example:
1.
H 3C CH2 CH3
i. O3
C C ii. H2O/Zn
H H
2-pentene
10
2.
CH2CH3
i. O3
CH3 C CH CH2 CH3 ii. H2O/Zn
3-methyl-3-hexene
3.
CH3
i. O3
ii. H2O/Zn
4-methylcyclopentene
11
c) Hydration of Alkynes (keto-enol tautomerism)
OH O
H2SO4
R C C R 1 + H 2O R C CH R1 R C CH2 R1
HgSO4
Enol Keto
Example:
H2SO4
H C C H + H 2O
HgSO4
ethyne
H2SO4
H 3C C C H + H 2O
HgSO4
propyne
12
d) Friedel- Crafts Acylation
ketone.
Example :
O
AlCl3
+ CH3 C Cl
O O
AlCl3
+ R C O C R'
13
e) Hydrolysis Geminal Dihalides
CHO
CH3 CHCl2
2Cl2 H2O
uv
Example :
14
17.4 Chemical Properties
A) Nucleophilic addition
R + -
C O
R1
aldehyde or ketone
(R or R1 may be H)
General reaction :
OH
R
C O + Nu R C Nu
H
H
15
General Mechanism
16
a) Addition of Hydrogen Cyanide
OH
R
C O + HCN R C CN
H
H
cyanohydrins
OH
R
C O + HCN R C CN
R1
R1
17
Example:
CN
CHO H C OH
NaCN
H2SO 4
Mechanism:
18
Exercises.
1.
O NaCN
H3C C H
H2SO 4
2.
O NaCN
H3C C CH3
H2SO 4
19
b) Addition of Grignard Reagent
General mechanism :
20
Grignard reagents react with carbonyl
+
H
CH3CH2CH2CH2MgX
+ HCOH
21
Reaction of Grignard reagent with aldehyde
CH2CH2CH3
H+
CH3 CH2MgX + HC O
tertiary alcohol
CH2CH3
H+
CH3CH2CH2MgX + C O
CH3
22
c) The Hydration Reaction
O R
H+
H C R + H2O HO C H
OH
O R
H+
R' C R + H2O HO C R'
OH
23
Example:
1.
O
H+
H C CH3 + H2O
ethanal
2.
O
H+
H C H + H2O
methanal
3.
O
H+
CH3 CH2C CH3 + H2O
2-butanone
24
Mechanism :
O
H+
H 3C C CH3 + H2O
propanone
25
d) The Addition Of Alcohols: Hemiacetals and
Hemiketals
hemiacetal.
O OH
R C H + R'OH R C OR'
H
hemiacetal
atom.
26
Ketone undergoes similar reaction to give
hemiketal.
O OH
R C R' + R''OH R C OR''
R'
hemiketal
ketal.
OH + OR''
H
R C OR' + R''OH R C OR'
H H
hemiacetal acetal
27
OH + OR'''
H
R C OR'' + R'''OH R C OR''
R' R'
hemiketal ketal
28
Example:
1.
H
HCl
CH3 CH2 CH2 C O + CH3CH2CH2OH
2.
OCH2CH2CH3
HCl
CH3 CH2 CH2 C OH + CH3CH2CH2OH
H
29
3.
CH3
HCl
CH3 CH2 C O + CH3CH2CH2OH
4.
OCH2CH2CH3
HCl
CH3 CH2 C OH + CH3CH2CH2OH
CH3
30
e) Addition of Sodium bisulfite
_
+
O Na OH
_ +
C O + NaHSO3 C SO3H C SO3 Na
Example:
1.
CH3
C O + NaHSO3
31
2.
H
32
Addition of Ammonia and its derivatives.
General reaction
H3O+
C O + H2N-Z C N-Z + H2O
Example:
33
R NH2 C NR
amine 10 imine
H2N NH2 C NNH2
hydrazone
hidrazina
H2N OH C NOH
oxime
C O hidroxylamine
H 2N NH C NNHC6H5
phenylhydrazine phenylhydrazone
O O
H2N NH C NH2 C NNH C NH2
semicarbazide semicarbazone
H2N NH NO2
C N NH NO2
O2N
O2 N
2,4-dinitrophenylhydrazine
2,4-dinitrophenylhydrazone
34
(Brady’s reagent)
35
When react with hydrazine, phenylhydrazine or
2,4-dinitrophenylhydrazine gives yellow precipitate
which is used as a test to determine the carbonyl
compounds.
a) Oxidation
Example :
O O
H+
CH3 (CH2)4 C H + K2Cr2O7 CH3 (CH2)4 C OH
36
b) Reduction
a) H2, Ni @ Pt
b) NaBH4 (sodium borohydride)
c) LiAlH4 (litium aluminium hydride)
O OH
H2, Ni
R C H R C H
aldehyde H
alcohol 10
37
O OH
H2, Pt
R C R1 R C R1
ketone H
alcohol 20
Example:
1.
O
LiAlH4
CH3 C H
H+
ethanal
2.
O
NaBH4/H+
CH3 C CH3
or H2/pt
propanone
38
Some tests to determine carbonyl compounds
39
3 Tollens’ To determine + : silver
[Ag(NH3)2] +,OH -
aldehyde mirror
40
CH3
|
-C-OH
|
41
CARBOXYLIC ACID AND
ITS DERIVATIVES
1
Structure
R C OH
RCOOH or RCO2H
(R ≡ alkyl, aryl or H)
2
NOMENCLATURE
3
IUPAC Nomenclature &
Common Name
CH3CH2CH2COOH CH3CH2CH2CH2COOH
Butanoic acid Pentanoic acid
Butyric acid Valeric acid
4
IUPAC Nomenclature
5
Br CH3 O
CH3 CH CH CH2 C OH
4-bromo-3-methylpentanoic acid
CH3 O
O CH3
HO C CH2 CH CH CH CH3
5-methyl-3-hexenoic acid
6
• Two COOH groups, the compound will be named as
alkanedioic acid’
(Example: ethanedioic acid, propanedioic acid and etc)
O O
7
O CH3 O
H CH2 COOH
C C
HOOC CH2 H
8
• When R is an aryl group, the parent name is benzoic
acid
Cl COOH
4-chlorobenzoic acid
9
• An aromatic dicarboxylic acid is named as
1,x-benzenedicarboxylic acid
HOOC
COOH
COOH
2-isopropyl-1,4-benzenedicarboxylic acid
10
• A cyclic carboxylic acid is named as cycloalkanecarboxylic
acid
1 COOH
cyclopentanecarboxylic acid
11
1 COOH
cyclohexanecarboxylic acid
CH3
Br 1 COOH
4-bromo-2-methylcyclohexanecarboxylic acid
12
A cyclic dicarboxylic acid is named as
1,x-cycloalkanedicarboxylic acid
COOH
COOH
1,2-cyclohexanedicarboxylic acid
COOH
Cl COOH
4-chloro-1,2-cyclohexanedicarboxylic acid
13
• When a compound contains a carboxyl group and other
functional group(s), the priority is given to the carboxylic
acid as the parent name.
COOH
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 H O
R C C R
O H O
Hydrogen bond
17
Solubility
a) Solubility in water
O H O H O
R C H C R
O H O H O
18
• The solubility of carboxylic acid in water is almost
the same as alcohol.
O
hydrophilic
hydrophobic R C OH
19
• Aromatic carboxylic acids are slightly soluble in
water due to the huge aromatic ring.
20
Example : Descending order of solubility
COOH COOH
>
CH3 CH2 CH2 CH2
21
b. Solubility in non polar solvent
O H O
R C C R
O H O
22
Acidity of Carboxylic Acid
• The acidity of carboxylic acid is influenced by:
i. Resonance effect
ii.Inductive effect
23
Resonance Effect
O
Carboxylate ion : R C O-
O-
Phenoxide ion :
24
• Carboxylic acids are more acidic due to the resonance
stabilisation of the carboxylate ion.
25
• Carboxylic acid is relatively a weak acid, however it is
stronger than phenol & alcohol
OH
> H2O
R C OH > > R OH
26
-
O O O
R C + H2O ⇌ R C
-
R C + H3O+
OH O O
carboxylic acid carboxylate ion
(resonance structure)
-
OH + H2O ⇌ O +
H3O+
phenol phenoxide ion
(resonance structure)
• Acidity :
– CH3CHCl-COOH > CH3CH2COOH
31
iii) Number of electron-attracting group in
the compound.
• Example:
CH3C(Cl)2-COOH and CH3CHCl-COOH
32
iv) The position of electron-attracting group
• Example:
CH3CH2CH(Cl)COOH and CH2(Cl)CH2CH2COOH
• Acidity :
CH3CH2CH(Cl)COOH > CH2(Cl)CH2CH2COOH
33
(v ) The inductive effect of electron- releasing
(electron-donating) group in the compound
• Example:
CH3COOH and CH3CH2COOH
35
1. Oxidation of primary alcohol and aldehyde
H R R
oxidizing oxidizing
R C OH agent C O agent C O
H H HO
1o alcohol aldehyde carboxylic acid
oxidizing
R agent COOH
Cl Cl
CH3
KMnO4 , H+
CH CH3 Δ COOH
+ CO2 + H2O
37
3. Formation and Hydrolysis of nitrile
NaCN H2O,H+
R CH2 X R CH2 CN R CH2 COOH
NaCN H2O,H+
38
4. Carbonation of Grignard Reagents
CO2
H2O, H+ + Mg(OH)Br
39
CHEMICAL PROPERTIES OF
CARBOXYLIC ACIDS
40
• Main reactions of carboxylic acid,
a. The reaction that involves the donation of H+
from –OH group.
b. The reaction that involves the substitution of OH
group
c. The reaction that involves the reduction with
LiAlH4 to primary alcohol
41
a. The reaction that involves the donation of
H+ from –OH group
1. Neutralisation
• Carboxylic acids are acidic, it can react with base such as
NaOH (aq) to give metal carboxylate salts,
O O
R C + NaOH R C + H2O
-
OH O Na+
42
COOH COO– Na+
+ NaOH + H2O
Sodium benzoate
43
2. Reaction with electropositive metals such as Na,
K, Ca, Mg and Fe.
O O
R C OH + M R C O M + H2
Exercise:
Cl O
C
OH
+ K
44
b. The reaction that involves the substitution
of –OH group (to form its derivatives)
1. Acid chloride formation
Acid chloride can be prepared from the reaction of
carboxylic acids with thionyl chloride, SOCl2 ; phosphorous
pentachloride, PCl5 ; phosphorous trichloride, PCl3
O
SOCl2
R C Cl + SO2 + HCl
O O
PCl5
R C OH R C Cl + POCl3 + HCl
O
PCl3
R C Cl + H3PO3 45
Exercise :
SOCl2
O
PCl5
CH3 CH C OH
CH3
PCl3
46
2. Esterification
Carboxylic acids react with alcohols in the presence of mineral
acid catalyst to produce esters.
O O
H+
R C OH + H—OR’ ⇌ R C O R' + H2O
carboxylic acid alcohol ester
O O
+ H2O
47
3. Acid anhydride formation
Acid anhydrides can be prepared from carboxylic acids by
the loss of water through heating.
O O O O
R C OH + HO C R heat R C O C R + H2O
acid anhydride
O O O O
heat CH3 C O C CH3
CH3 C OH + CH3 C OH
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 O
RNH2
R C Cl R C NHR + H2O
(1o amine) 2o amide
O
R2NH
R C NR2 + H2O
(2o amine)
(3o amide)
49
Exercise :
NH3
CH3 O
CH3 NH2
CH C Cl
CH3
CH3 NH
CH3
50
c. The reaction that involves the reduction with
LiAlH4 to primary alcohol
LiAlH4
R C O R' R CH2 OH + R’OH
ether
1o alcohol
O
LiAlH4
CH3 CH C O CH2 CH3 ether CH3 CH CH2 OH
CH3 CH3
+ HO—CH2CH3 51
Methanoic acid, HCOOH as a reducing agent
O O
and
C OH H C
carbonyl
carboxylic
52
KMnO4 / H+
O CO2 + H2O + MnO2
(Brown)
H C OH
Ag(NH3)2+ Ag + CO2 + H2O
53
DERIVATIVES OF
CARBOXYLIC ACIDS
54
Reactions of carboxylic acid derivatives
i. Hydrolysis of acid chlorides
O O
H2O
R C Cl R C OH + HCl
acid chloride carboxylic acid
O O O
H2O
R C O C R 2 R C OH
acid carboxylic acid
anhydride
55
Reactions of carboxylic acid derivatives
iii. Hydrolysis of esters
H2O
O H+ + ROH
carboxylic acid alcohol
R C OR
O
ester
H2O -
NaOH R C O Na
+ + ROH
alcohol
56
Example :
O
H2O
C Cl
benzoyl chloride
O O
H2O
CH3 C O C CH3
ethanoic anhydride
57
Example :
O
H2O
CH3 C O CH3
H+
methyl ethanoate
58
Relative Reactivity Of Carboxylic Acid
Derivatives
• The reactivity of a carboxylic acid derivative depends
on the basicity of the substituent (leaving group) that
attached to the acyl group
59
Relative basicities of the leaving group (substituent)
O O O O O O
R C Cl , R C O C R , R C OR , R C OH , R C NH2
acid acid ester carboxylic amide
chloride anhydride acid
reactivity increases
60
ACYL CHLORIDE
61
ANHYDRIDE ACID
O O
R C O C R'
• This makes the carbonyl carbon becomes more
electropositive and can be easily attack by
nucleophile.
62
ESTER
63
AMIDE
R H R H
+
N N
-
O H O H
64
The Uses of Carboxylic Acid
Carboxylic acid / derivatives Uses
Polyamide (Nylon) carpet, apparel
Ester Artificial flavors
Acetic acid Vinegar
Ethanoic anhydride Drug aspirin
Salicylic acid analgesic
65
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.1 Introduction
Amines are organic derivatives of
ammonia, NH3
Classification of Amines
Primary amines H N H
R
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.2 Examples:
CH3 N-ethyl-N-methyl
CH3CH2 N CH2CH3
ethanamine
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
Examples:
NH2CH2COOH 2-aminoethanoic acid
2 1
H 2N 4
1 OH
3 2 2,4-diaminophenol
NH2
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
N-ethyl-N-methylaniline
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
CH3NHCH2CH3 methylethylamine
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.3 Basicity
An amine is a nucleophile (a Lewis base)
base
Boiling point
because its lone pair of non-bonding
Solubility electrons on nitrogen
H H
Basicity
+ -
H N + H OH H N H + OH
H H
Ammonia Ammonium ion
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
H H
1° Amine alkylammonium ion
Stabilised by the
alkyl group Stronger base
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.3 H H
+ -
R N + H OH R N H + OH
Boiling point
H H
Solubility 1° Amine alkylammonium ion
Basicity R R
+
R N + H OH R N H + OH
H H
2° Amine alkylammonium ion
Basicity Example:
NH2 NH2
Cyclohexylamine Aniline
pKb = 3.36 pKb = 9.42
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.4 Example :
Reduction of O H
i.
1. LiAlH 4
nitro compound CH3 C NH 2 CH3 C NH 2 + H2O
+
2. H
Reduction of H
Ethanamide
nitriles Ethanamine
(2o amide)
(1o amine)
Reduction of
amides ii.
O CH3 1. NaBH4
H CH
3
+ CH3 C NH + H2O
Hoffmann’s CH3 C NH 2. H
H
degradation of
amides N-methylethanamide N-methylethanamine
(2o amine)
(2o amide)
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.4 Example :
R N H + CH3 C O C CH 3 R N C CH 3
Acid anhydride
1o amine acid anhydride 2o amide
Benzenesulphonyl
chloride + CH3COO H
R O O R O
Nitrous acid
R N H + CH 3 C O C CH 3 R N C CH3
Bromine water 2o amine acid anhydride 3o amide
+ CH3COO H
Nitrous acid
Bromine water
Formation of dye
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.5 1° amines
Reaction with : Benzenesulphonyl chloride reacts with a
1° amine to form a white precipitate
Acyl chloride (N-substituted sulphonamides)Acidic hydrogen
Acid anhydride H O H O
-
+ OH R-N -S-
Benzenesulphonyl R-N-H Cl-S-
chloride (-HCl)
O
1o amine O
Nitrous acid N-substituted
Na O benzenesulphonamides
Bromine water R-N -S- (precipitate)
N-substituted sulphonamides have an
O
acidic hydrogen, N-H.NaOH
Formation of dye wateritsoluble salt in aqueous NaOH.
Therefore, dissolve
(clear solution)
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.5 2° amines
Reaction with : Benzenesulphonyl chloride reacts with a
2° amines to form a white precipitate
Acyl chloride (N,N-disubstituted sulphonamide)
R' O R' O
Acid anhydride -
+ OH
Benzenesulphonyl R-N-H Cl-S- R-N -S-
chloride (-HCl)
o O
2 amine O
Nitrous acid N,N-disubstituted
benzenesulphonamides
Bromine water (precipitate)
N,N-disubstituted sulphonamides do not
No reaction
have an acidic hydrogen, N-H.NaOH
Formation of dye
Therefore, it dissolve in aqueous NaOH.
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.5 3° amines
Reaction with : 3° amine do not gives visible reaction
with benzenesulphonyl chloride
Acyl chloride
Summary of Hinsberg’s test:
Acid anhydride
NaOH
Benzenesulphonyl 1° amines white precipitate clear
chloride solution
NaOH
Nitrous acid 2° amines white precipitate do not
dissolved
Bromine water
3° amines do not give any visible
Formation of dye change
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
Formation of dye
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
Bromine water
Formation of dye
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.5 Identification
Reaction with bromine water
test
Reaction with : Aniline reacts with aqueous bromine to
yield white precipitates
Acyl chloride
NH2 group is an activating and ortho-
Acid anhydride para directors group
Benzenesulphonyl NH2 NH2
chloride
3Br2(aq) Br Br
Nitrous acid
room temperature + 3HBr
Bromine water
Br
(2,4,6-tribromoaniline)
Formation of dye
Observation: White precipitate formed
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature
19.5
Reaction with :
Acyl chloride OH
N=N OH
Bromine water
Formation of dye
Chapter 20 : Amino Acids and Proteins
20.1
-amino acid
20 amino acids
Naming
Zwitterion
Isoelectric point
Structures in:
Acidic
Basic
pI
Chapter 20 : Amino Acids and Proteins
pI CH 2 CH 3
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
20 amino acids Glycine H CH COOH
Naming Gly NH2
Zwitterion
Alanine H3C CH COOH
Isoelectric point
Ala NH2
Structures in: CH 3
Valine
Acidic Val HC CH COOH
Basic CH 3 NH 2
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
C H
20 amino acids Leucine 3
C H C H C H C O O H
Naming Leu 2
C H 3 N H 2
Zwitterion
Isoleucine CH 3CH 2CH CH COOH
Isoelectric point Ile CH 3
NH2
Structures in:
Phenylalanine
Acidic Phe CH2 CH COOH
NH2
Basic
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
OH
20 amino acids Threonine
CH 3 C CH COOH
Naming Thr
H NH 2
Zwitterion CH 2 CH 2 COOH
Cysteine
Isoelectric point C
Cys CH 2 NH
Structures in: H
Methionine
Acidic HO CH2 CH COOH
Met
Basic NH2
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
O
20 amino acids Tryptophan
OH
Naming Trp NH2
NH
Zwitterion CH 2 CH 2 COOH
Proline
Isoelectric point C
Pro CH 2 NH
Structures in: H
Serine
Acidic HO CH2 CH COOH
Ser
Basic NH2
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
Threonine OH
20 amino acids CH3 C CH COOH
Thr
Naming H NH 2
Zwitterion Cysteine HS CH2 CH COOH
Isoelectric point Cys NH2
Structures in:
Methionine CH S CH CH CH COOH
3 2 2
Acidic
Met NH2
Basic
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
20 amino acids Tyrosine HO CH2 CH COOH
Naming Tyr NH2
Zwitterion
Asparagine NH2─C─CH2─CH ─COOH
Isoelectric point ║ │
Asn O NH2
Structures in:
Glutamine NH2─C─CH2CH2─CH─COOH
Acidic ║ │
Gln O NH2
Basic
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
Aspartic HOOC─CH2─CH─COOH
20 amino acids
acid │
Naming NH2
Asp
Zwitterion Glutamic HOOC─CH2CH2─CH─COOH
Isoelectric point acid │
NH2
Structures in: Glu
Acidic Lysine H2N─CH2CH2CH2CH2─CH ─COOH
Lys │
Basic NH2
pI
Chapter 20 : Amino Acids and Proteins
20.1
Name Structure
-amino acid
Arginine H2N─C─NH─(CH2)3─CH─COOH
20 amino acids │ │
Arg NH NH2
Naming
Zwitterion
Histidine HC─C=CH2─CH ─ COOH
│ │ │
His N NH NH2
Isoelectric point
Structures in: CH
Acidic
Basic
pI
Chapter 20 : Amino Acids and Proteins
iii) CH2OH
Acidic 3
H C COOH 2-amino-3-hydroxy
Basic 2 1
propanoic acid
NH2
pI
Chapter 20 : Amino Acids and Proteins
pI
Chapter 20 : Amino Acids and Proteins
20.1 Zwitterion
-amino acid Amino acids can undergo an
internal acid-base reaction, in which a
20 amino acids proton is transferred from the
Naming carboxyl (-COOH) to the amino group
(-NH2) to form dipolar ion called
Zwitterion
zwitterion.
Isoelectric point
CH2CH2CH3 CH2CH2CH3
Structures in: -
H C COOH H C COO
Acidic NH2 +
NH3
Basic
(neutral) (dipolar ion @
pI zwitterion)
Chapter 20 : Amino Acids and Proteins
20.2
Reactions of
–NH2 group:
HCl
HNO2
Reactions of
-COOH group:
NaOH
ROH
Peptide bond
Importance
Chapter 20 : Amino Acids and Proteins
HNO2
Example:
Reactions of CH2CH3 CH2CH3
-COOH group: + _
H C NH2 + HCl H C NH3Cl
NaOH COOH COOH
ROH
Peptide bond
Importance
Chapter 20 : Amino Acids and Proteins
NaOH COOH
carbocation
ROH H 2O - +
+ Cl -H
Peptide bond 2-hydroxy halocarboxylic Alkenoic
carboxylic acid acid acid
Importance
Chapter 20 : Amino Acids and Proteins
HNO2
Example:
Reactions of
CH2CH3 CH2CH3
-COOH group:
H C NH2 + NaOH H C NH2
NaOH _
COOH COO Na+
ROH
Peptide bond
Importance
Chapter 20 : Amino Acids and Proteins
HNO2
Example:
Reactions of
CH2CH3 R'
-COOH group: HCl
H C NH2 + CH3OH R C NH2 + H 2O
NaOH
COOH COOR''
ROH
Peptide bond
Importance
Chapter 20 : Amino Acids and Proteins
O H O CH2 OH
H2N CH2 C N C C N C COOH
H CH3 H H
A tripeptide
Chapter 20 : Amino Acids and Proteins
POLYMERS
FJ/Chemistry Unit, KMPk/Mac 2006 1
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
- Example :
ethene polyethene
(ethylene) (polyethylene)
3
Copolymer
- a polymer formed from two or more different monomers.
nA + nB -A-B-n
- Example :
4
21.2 : Structures of Polymers
21.2.1 : Linear Polymers
Linear polymer is a polymer consist of monomers that are
linked in straight and long continuous chain.
Linear or straight-chain polymer can be folded back upon
themselves in a random fashion.
Linear polymer is recycleable because it is soft and can be
reformed when heated.
-A-A-A-A-A-A-A-A-n
monomers link together
in a straight chain
folded linear polymer
in a random fashion
5
21.2.2 : Cross-linked Polymers
-A-A-A-A-A-A-A-A-A-A-A-A-
X X
-A-A-A-A-A-A-A-A-A-A-A-A-
• Long polymer chain cross-linked by branched
CH3 CH3
-CH2C CH-CH2- + -CH2C CH-CH2-
sulphur
CH3 CH3
-CHC CH-CH2-CHC CH-CH2-
S S
-CHC CH-CH2-CHC CH-CH2-
CH3 CH3
After vulcanization rubber becomes more stable over wide
ranges of temperature and far more durable than natural
rubber.
7
21.3 : Types of Polymers
21.3.1 : Natural Polymers
Natural polymers are polymers that synthesized in nature
or naturally occurring polymers.
i. 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 n
8
ii. Carbohydrates
Carbohydrates such as starch is also a polymer.
i. Starch (amylose)
CH2OH CH2OH
O O
H H HH H H
O OH H O OH H O
H OH H OH
n
α-(1,4)-glycosidic linkages
n CH2=C-CH=CH2 -CH2-C=CHCH2-
CH3 CH3 n
isoprene cis-polyisoprene
i. Formation of polyethene
n HC CH2 ROOR (
-HC-CH 2-
)n
Cl Cl
chloroethene polychloroethene
(polyvinyl chloride or PVC)
12
iii. Formation of polystyrene
n HC CH2 ROOR (
-HC-CH 2-
)n
phenylethene Polyphenylethene
(styrene) (polystyrene)
14
(A). Polyamides
i. Formation of Nylon 6,6
O O
n H2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH
hexane-1,6-diamine hexane-1,6-dioic acid
H H O O
(
-N-(CH 2)6-N-C-(CH2)4-C-
)n + n H2O
Nylon 6,6
H H O O
N- -N-C- -C n + n HCl
Kevlar
(B). Polyester
i. Formation of Dacron
O O
n CH3O-C- -C-OCH3 + n HO-CH2CH2-OH
1,2-ethanediol
dimethyl terephthalate
(ethylene glycol)
O O
(
-O-CH 2CH2-O-C- -C-
)n + n CH3OH
17
ii. Formation of Terylene
O O
n HO-CH 2CH 2-OH + n HO-C- -C-OH
ethane-1,2-diol benzene-1,4-dicarboxylic acid
O O
(
-O-CH 2CH 2-O-C- -C-
)n + n H 2O
water
Terylene
18
21.4 : Uses of Synthetic Polymers
19