Chapter 5 Organic Spectroscopy.

V Semester (organic) notes prepared by Dhondiba V.Suryawanshi, GCW Kolar.
Chapter 5: Spectroscopy of Organic compounds 8 hours
UV-Visible spectroscopy: Introduction. Chromophores and auxochormes; blue

shift and red shift. Graphical representation of spectra of 1,3-butadiene,
benzene and lycopene. Influence of conjugation on UV absorption-Comparison
of UV spectra of acetone and methyl vinyl ketone.
IR spectroscopy: Introduction. Stretching frequencies of OH (free and H-

bonded), alkyl CH, CC, C=C, CC, C=O and CO groups (by taking suitable
examples). Graphical representation of IR spectra of benzoic acid and methyl
benzoate.
NMR spectroscopy: Basic principles of proton magnetic resonance: Nuclear

magnetic spin quantum number I, influence of the magnetic field on the spin of
nuclei, spin population, saturation using radio frequency. Nuclear magnetic
resonance. chemical shift ( values), uses of TMS as reference. Nuclear
shielding and deshielding effects. Equivalent and non-equivalent protons.
Effect of electronegativity of adjacent atoms on chemical shift values. Spin-
spin splitting and spin-spin coupling (qualitative treatment only).
Applications of NMR spectroscopy including identification of simple organic

molecules. Examples: Shielding and deshielding effects for (i) methane (ii)
CH3Cl (iii) CH2Cl2 (iv) CHCl3. Spin-spin coupling in (i) Cl2CHCHO (ii)
1,1,2-trichloroethane (iii) CH3CH2Cl.
Introduction to spectroscopy:
Spectroscopy: The techniques which are used to determine the whole structure
of the light unknown compounds with interacting of light (electromagnetic
radiations) called spectroscopy.
Advantages of spectroscopy:
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Spectroscopy need very little time and the information obtained is often a
permanent record in the form of a chart.
In spectroscopy, the substance is required in very small quantities.
Spectroscopy extremely sensitive and the information obtained is highly
reliable.
Spectroscopy can be detected and identity of even very short lived
reaction intermediates.
Spectroscopic methods are non destructive and, if necessary, the entire
sample can be recovered.
Electromagnetic radiations: All types of radiations varying both electric and
magnetic properties and they travels in the form of waves called
electromagnetic radiations. These radiations are considered as a stream of
energetic particles called photon or wave motion. The fundamental equations of
electromagnetic radiations are E =h and C =
Where, E = Energy of radiation h = Planck constant = 6.626 x 10-34 js
= Wavelength of the radiation C = Velocity of light = 3 x 108 cm s-1
Electromagnetic spectrum: Arrangement of all electromagnetic radiations in
the form of increasing order of frequency or decreasing order of wavelength or
vice - versa called electromagnetic spectrum. The partial electromagnetic
spectrum can be drawn below.
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Electromagnetic Radiation Interact with Matter (Atoms, Molecules) =

Spectroscopy
Principle of spectroscopy: All organic compounds interact with
electromagnetic radiation, i.e. they absorb energy. When a molecule absorbs
energy, a transformation occurs that may be either temporary or permanent.
Lower energy radiations may cause a molecular rotation or bond vibration;
higher energy radiation may cause the promotion of electrons to higher energy
levels or bond cleavage.
Whether the transformation involves molecular rotation, bond vibration or
electronic transformation, the molecule absorbs only the wavelength of
radiation with exactly the energy necessary for the transformation. The
absorption of wavelengths of radiation is selective for a particular transition
which depends on the structure of the molecule. By measuring the absorption
spectra of known compounds we can correlate the wavelengths of energy
absorbed with characteristic structural features. This information is then used
to determine the structure of unknown compounds.
Spectrophotometer: The instrument is used to measure the amount of
electromagnetic radiation absorbed by an organic molecule is called
spectrophotometer or spectrometer. It consists of a light source of radiation
with a prism that can select the desired wavelengths, which are passed
through a sample of the compound being investigated. The radiation that is
absorbed by the sample can be detected, analyzed and recorded. The recording
is called the spectrum of the compound.
There are three types of spectroscopy according to the syllabus.
1) Ultra violet visible spectroscopy
2) Infra red spectroscopy
3) Nuclear magnetic resonance spectroscopy.
Ultra- violet visible spectroscopy
Introduction: The technique which is used to determine the structure of the
organic compounds by interacting organic compound with electromagnetic
radiations (light) having the wavelength 200 nm 800 nm called ultraviolet
3
visible spectroscopy. These radiations having the sufficient energy to

transformation of electrons like sigma ( ), pi ( ) and non bonding (n) from the
ground state to the higher energy state.
Types of electronic transitions: According to the molecular orbital theory
when a molecule is excited by the absorptions of energy (UV or visible light), its
electrons are promoted from a bonding to an anti bonding orbital. Therefore
there are four types of electronic transitions are possible in ultraviolet visible
region.
1) * transitions: This type of transition involved in the saturated

hydrocarbon compounds. This bond is formed by face to face overlapping and
which is strong one. Also the energy gap between bonding sigma orbital ( )
electrons and anti bonding sigma orbital ( *) electron is large. So this type of
transition required higher energy radiation. UVVisible radiations not having
sufficient energy to this type of transition. But this type of transition gives the
absorption band at far ultra violet region (126nm 135nm). Therefore *
transition cannot be study in UV Visible region.
2) n * transition: This type of transition involved in the saturated

compounds with lone pair (non-bonding) electrons. In addition to *
transition, the energy required for n * transition is generally less that
required for * transition. Also the energy gap between non bonding
electron orbital to anti bonding sigma orbital is less compare to *
transition. Again, UV Visible radiation not having sufficient energy to take the
transition of
n *. But this type of transitions gives the absorption band at near

ultraviolet visible region (180 -200 nm). Therefore n * transition cannot be
study in ultra violet visible region.
3) * transition: This type of transition involved in the unsaturated

hydrocarbon compounds. Since bond is formed by lateral overlapping and
which is weak one. Also the energy gap between bonding pi orbital () electrons
and anti bonding pi orbital (*) is less. So this type of transition required lower
energy radiation. UV- visible radiation having sufficient energy to this type of
transition. Therefore, this type of transition can be study in UV- visible region.
When compound absorbs the UV radiation by making the transition from
4
* absorption peaks are observed. This type of transition depends on

selection rule to decide the transition allowed or forbidden.
4) n * transition: This type of transition involved in the unsaturated

compounds which contain atoms such as oxygen, nitrogen and sulphur. Since
non bonding (n) electrons not participate in band formation. So these electrons
required least energy radiation to take the transition from non bonding orbital
to anti bonding pi orbital. Therefore ultraviolet visible radiation has sufficient
energy to make the transition of n *.
These transitions are generally
observed the UV visible radiation in the range 270 350 nm.
A graph of energy against electronic transition can be summarizes below.

Energy
n
n - n-
Chromophores: Any multiple bonded group which exhibits absorption of

electromagnetic radiations in the visible or ultra violet region, it may or may
not impart any colour to the compound is called chromophores.
For example
O
-N = N - -N=O -N=O
Diazo Nitroso Nitro
p - quinone o - quinone
Auxochromes: A saturated group which itself does not act as a chromophore

but when attached to a chromophore, shifts the absorption maximum towards
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longer wavelength along with an increase in the intensity of absorption called

auxochromic group or auxochrome.
For example NH2, -OH, -NHR, -SH, OR.
Bathochromic shift (red shift): A shift of max absorption to a longer
wavelength in presence of auxochrome group called bathochromic shift or red
shift.
For example, in phenol and aniline the OH and NH2 group act as auxochrome,
as their non bonded electrons interact with the pi bonds of the benzene ring
which leads to increase in max and max absorption.
OH NH2
benzene phenol aniline

max = 255 nm max = 270 nm max = 280 nm
Hypsochromic shift (blue shift): A shift of max absorption to a lower (short)

wavelength in presence or absence of auxochrome group called hypsochromic
shift or blue shift.
For example, addition of a proton to aniline decreases its max (blue shift).
+
NH2 NH3
aniline anilinium
max = 280 nm max = 250 nm
Influence of conjugation on max absorption: Conjugation of double bands

lowers the energy required for the transition. The reason is that in conjugated
systems, the difference in energy between the highest occupied molecular
orbital (HOMO) and the lowest vacant anti bonding molecular orbital (LUMO)
becomes smaller.
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LUMO
LUMO

HOMO HOMO
- CH = CH - CH - CH = CH - - CH = CH - CH = CH - CH =
Non cojugated pi electrons Conjugated pi electrons
As a result CH=CH-CH=C and CH=CH- C=O exhibit *

absorption bands within the ordinary ultraviolet range. For instance, 1,3-
butadiene (-CH2=CH-CH=CH2-) in hexane solution shows max 217 nm. As
the number of double bonds in conjugation increases, the absorption moves to
longer wavelengths. Thus spectrum of 1, 3, 5, 7-octatetriene (-CH2=CH-
CH=CH-CH=CH-CH=CH2-) in hexane exhibits max 296 nm. If there are
enough double bonds in conjugation absorption will ultimately move into the
visible region and the compound will be coloured. For example, carotene, a
naturally occurring yellow pigment containing 11 double bonds in conjugation
owes its colour to absorption in the visible part of light max is 451 nm.
H3C
CH3 CH3
H3C CH3
H3C CH3
CH3 CH3
CH3
Carotene
Aldehydes and ketones have two absorption bands in the ultraviolet region.
Both involve excitation of an electron to an anti bonding * orbital (n* and
* ).
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In case of acetone, it contains one pair pi bonding and two pair non bonding
H3C
..
C O max187 nm
..
H3C
n * max nm
electrons
max nm
max187 nm
n n

Excited state Excited state
n

Ground state
H3C
..
C O
..
H3C
They involved * and n * are takes place. * transition

require more energy and the absorption peak appears at 187 nm, whereas
n * transition require less energy and its absorption peak appears at
longer wave length 270 nm.
The graphical representation of acetone is given below.
8
UV-Visible spectra of acetone

max 270 nm
max 187 nm
Extinction coefficient max
due to n
due to
180 280 320

200 220 240 260 300
wavelength in nm
Now, the vinyl methyl ketone is conjugated molecule of acetone. Due to

presence of conjugated pi bond it shifts the to * transition towards longer
wavelength and appears at 219 nm and n to n* transition towards longer
wavelength and it appears at 324 nm.
i.e.
O
H2C CH C CH3
max = 219 nm and max = 3600
n max = 324 nm and max = 24
The graphical representation of methyl vinyl ketone is given below.
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UV-Visible spectra of methyl vinyl ketone
max 219 nm
due to max 324 nm

Extinction coefficient max
due to n
200 260 380

220 240 280 300 320 340 360
wavelength in nm
Also, compounds in which the carbon-oxygen double bond is conjugated with a

carbon-carbon double bond have absorption maxima corresponding to n*
excitation and * excitations.
The n* absorption maxima occur at larger wavelengths but are much
weaker (i.e.,smaller molar absorptivities)
O
H2C CH C CH3
max = 219 nm and max = 3600
n max = 324 nm and max = 24
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Graphical representation UV-Visible spectra of 1, 3- butadiene:
The diagram below shows a simple UV-visible absorption spectrum for buta-
1,3-diene - a molecule. Absorbance (on the vertical axis) is just a measure of
the amount of light absorbed. The higher the value, the more of a particular
wavelength is being absorbed.
You will see that absorption peaks at a value of 217 nm. This is in the ultra-
violet and so there would be no visible sign of any light being absorbed - buta-
1,3-diene is colourless. You read the symbol on the graph as "lambda-max".
In buta-1, 3-diene, CH2=CH-CH=CH2, there are no non-bonding electrons. That

means that the only electron jumps taking place (within the range that the
spectrometer can measure) are from pi bonding to pi anti-bonding orbitals.
Graphical representation UV-Visible spectra of benzene: Benzene is a

molecule which contain conjugation of pi bonds. Hence it absorbs
electromagnetic radiation at 256 nm due to to * transition.
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Absorbance max = 256 nm
200 220 240 260 280 300 320

Wavelength () in nm
Graphical representation UV-Visible spectra of lycopene: Structure of

lycopene as below.
H3C
CH3 CH3 CH3
H3C
CH3
CH3 CH3 CH3
CH3
It contains highly conjugated pi bond system. Hence it absorbs electromagnetic

radiation at 471
nm due to to * transition.
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max = 471nm
Lycopene
Lycopene
Absorbance
200 250 300 350 400 450 500 550

Wavelength () in nm
Absorption by Compounds with C=O Bonds

The carbonyl groups of saturated aldehydes and ketones give a weak
absorption band in the UV region between 270 and 300 nm.
Aldehydesand ketones have two absorption bands in the ultraviolet region.

Both involve excitation of an electron to an anti bonding * orbital (n* and
* ).
H3C
..
C O max187 nm
..
H3C
n * max nm
13
max nm
max187 nm
n n

Excited state Excited state
n

Ground state
H3C
..
C O
..
H3C
Infrared spectroscopy
Introduction: The technique which is used to determine the structure of

organic compound by interaction with light (electromagnetic radiation) in the
range of 2.5 m to 15.4 m (4000 cm-1 to 650 cm-1) called infrared
spectroscopy. These radiations have the insufficient energy to transformation of
electrons from bonding molecular orbital to anti- bonding molecular orbital.
But these have sufficient energy to electronic vibration, bending, and
stretching.
Principle of infrared spectroscopy: Electromagnetic radiations having the
range 2.5 m to 15.4 m are not energetic enough to cause electronic
excitations in most organic molecules, but they cause stretching and bending
of organic bonds. These results in a rich array of close packed absorption band
provide a wealth of structural information about the molecule.
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This technique is based upon the simple fact that a chemical substance
shows marked selective absorption in the infrared region. After absorption of
I.R radiations, the molecules of a chemical substance vibrate giving rise to
close packed absorption bands called an IR absorption spectrum.
The bond positions in an infrared spectrum may be expressed in terms of
wave number (
= and =
Wave number is the reciprocal of wavelength. Band intensities in IR spectrum

may be expressed either transmittance (T) or absorbance (A).
The ratio of radiant power transmitted by a sample to the radiant power
incident on the sample called transmittance. On the other hand, the logarithm
to the base 10 of the reciprocal of the transmittance is called absorbance.
A= )
Conditions for a molecule to give IR spectrum OR conditions for a

molecule to IR active.
The following conditions are
1) A natural frequency of vibration of the molecule must be equal to the
frequency of the incident radiation.
2) The change in bond length or bond angle due to vibrational or rotational
motion must cause a net change in the dipole moment of the molecule
3) The radiation energy must correspond to the energy difference of the ground
and excited state of the molecule.
Vibrational transitions: The absorption of infrared radiation having energy
equal to the difference between two vibrational energy levels will give rise to a
vibrational transition. In the transition from ground state to the first excited
state, light gets absorbed strongly and as a result intense bands called
fundamental absorption bands. The number of fundamental absorption bands
exhibited by a molecule is related to the fundamental vibrational modes of a
molecule.
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Stretching and bending modes of vibrations: The atoms containing a

molecule are not held rigidly. They are continuously rotating and vibrating in a
number of ways. These are two main kinds of vibrations these are,
1) Stretching vibrations: In this type of vibrations, the distance between the
two atoms increases or decreases but the atoms remain in the same bond axis.
In a simple diatomic molecule A B; the only vibrations which can occur is a
rhythmic compression and extension along the A B bond. This type of
periodic back and forth axis which can be compared to that of a coiled spring is
known as stretching vibration or bond stretching as shown in following figures.
Types of stretching vibrations: In tri atomic or higher molecules, the

stretching vibrations can be of
i) Symmetric stretching: In this type of stretching vibrations, the movement
of the atoms with respect to a central atom in the molecule is in the same
direction as shown in figure No.1
ii) Asymmetric stretching: In this type of vibrations, one atom moves towards
the central atom while the other moves away from it. As shown in figure No.1.
2) Bending vibrations: In this type of vibrations, the positions of the atoms
change with respect to the original bond axis. More energy is required to
stretch a strong than that required to bend it. Hence the stretching absorptions
of a bond appear at higher frequencies as compared to the bending absorption
of the same bond.
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Bending vibrations are the periodic changes in bond angles between bonds
formed by two atoms with a central atom as shown in figure No.1.
Figure No. 1
Types of bending vibrations:

1) Scissoring: In this type of bending vibrations, the movement of the two
atoms is towards each other as shown in figure No.1
ii) Rocking: In this kind of vibrations, the two atoms move in the same
direction as shown in figure No.1.
iii) Wagging: In this type of vibrations, the movement of the two atoms is either
up the plane or below the plane with respect to the central atom as shown in
figure No.1.
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iv) Twisting: In this type of vibrations, one atom moves up the plane while the
other moves down the plane with respect to the central atom as shown in figure
No.1.
Factors influencing on the position of absorption OR influence of force
constant and atomic weight on absorption positions:
The vibrations of a diatomic molecule may be considered analogous to those of
a simple harmonic oscillator. i.e. oscillator in which the force tending to restore
an atom to its original position is proportional to the displacement of the atom
from that position, in accordance with Hooks law. In other words a covalent
bond may be considered to be behaving as a weightless spring, the restoring
force F acting upon it when it is stretching to a distance (x) is given by Hooks
law. F = - k x, where k = force constant for of the bond.
The frequency of its vibration ( ) is given by
Where,
= Reduced mass of diatomic

molecule
and = masses of two atoms. C = Velocity of light.
Therefore, the two factors are influencing on the position of absorptions.
1) Atomic weight (mass): The smaller the constituent atoms of a diatomic
molecule or group, smaller is the reduced mass ( ) and therefore higher its
vibration frequency.
2) Force constant: The force (k) is a measure of the strength of the bond. As
the force constant increases, the bond order also increases and hence
vibrational frequency also increases. The vibrational frequency increases in the
order of C- C C= C C.
Position of absorption bands: The position of absorption band depends upon
the nature of the bond or group. Absorption band characteristic of a particular
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bond or group indicates the presence that bond or group in the molecule.
Similarly the absorbance of characteristic absorption bond of a bond or group
gives the absence of that particular bond or group.
1) Functional group region: Absorption bands of the functional group
observed in the range of 2.5 m to 8 m (4000 to 1600 cm-1) and are
associated with the change in the vibrational states of the various bonds. Most
of the functional groups show characteristic absorption bands in this region.
Hence this region is known as functional group region.
2) Fingerprint region: Absorbance bands of the health observed in the range

of 8 m to 15 m
(1600 cm-1 to 650 cm-1) are associated with complex vibrational and rotational
energy changes of the molecule as a whole called fingerprint region.
A peak by peak match of an unknown spectrum with the spectrum of the
suspected compound in this region can be used, much like a fingerprint, to
confirm its identity.
IR spectra of organic compounds with different functional groups:
Frequency range (cm-1) Functional group
1050 -1400 C O(in ethers, alcohols, esters)
1050 -1400 C N (in amines)
1315 -1475 C H (in alkanes)
1340 -1500 NO2 (Two Peaks)
1450 -1600 C = C (in aromatic ring, several peaks)
1620 - 1680 C = C (in alkanes)
1630 -1690 C = O ( in amides)
1690 -1750 C = O (in aldehydes, ketones, esters)
1700 - 1725 C = O (in carboxylic acids)
1770 -1820 C = O (in acid chlorides)
2100 -2200 C C
2210 -2260 C N
2500 S H
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2700 -2800 C H (of aldehyde group)

2500 -3000 O H (of COOH group)
3000 -3100 C H (C is the part of aromatic ring)
3330 C H (C is the part of C C)
3020 - 3080 C H (C is the part of C = C)
2800 -3000 C H ( in alkane)
3300 - 3500 N H (in amines, amides)
3200 -3600 O H (in hydrogen bonding R OH)
3600 - 3650 0 H (in absence of hydrogen bonding)
Graphical representation of IR spectra of benzoic acid:
20
Note: On Y axis = Transmittance and on X axis = wave number
Benzoic acid (C6H5COOH)
(3230-3550) O-H stretch Broad Absorption due to H bonding between

molecules
(2840-3000) C-H stretch
(1400-1500) C=C aromatic stretch
(1000-1300) C-O stretch
(1680-1740) C=O stretch

Graphical representation of IR spectra of methyl benzoate.
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Nuclear magnetic resonance spectroscopy:
Introduction: The technique which is used to determine the structure of

unknown compound by interaction with electromagnetic radiation having the
frequency 60 MHZ (in microwaves) or in magnetic field about 14000 gauss
called nuclear magnetic resonance spectroscopy.
Basic principles of proton magnetic resonance spectroscopy (nuclear
magnetic resonance spectroscopy): When a substance is placed in magnetic
field of constant strength and radiation of steadily changing frequency is
passed through it then a certain frequency the energy of radiation matches the
energy required to flip the proton. This radiation is observed and a signal is
observed. Plot of frequencies absorbed against field strength gives the nuclear
magnetic resonance spectrum.
Like electrons, the nuclei of certain atoms are considered to spin. The
spinning of these charged particles generated a magnetic moment along the
axis of the spin and hence the nuclei acts like a tiny bar magnet. One such
nucleus is the proton the nucleus of ordinary hydrogen 1H. Other examples are
13C called CMR. Proton nuclear magnetic resonance spectrum is also called the
PMR spectrum.
In an external magnetic field, the proton can be aligned in two ways i) with
the field and ii) against the field. The proton aligned with the field is more
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stable, where as to align it against the field i.e. to flip the proton energy is
needed.
spin state
against the field
Radom orientation
of spin (absence of Ho spin state
magnetic field) aligned with field
The energy required to flip the proton is not much and depends on the strength
of the field. In a field of about 14000 gauss, electromagnetic radiation of
frequency 60 MHz can supply the required energy. This corresponds to radio
waves.
Nuclear magnetic resonance spectra are observed to those nucleus having
total spin value I , Examples 1H, 19F, 31P, 13C. No spectra are observed with
nuclei having I = 0
Nuclear magnetic resonance: When a nucleus is placed in a system where it
absorbs energy. It becomes excited. It then loses energy to returns to the
unexcited state. It absorbs energy and again enters an excited state, this
nucleus which alternately becomes excited and unexcited is said to be in a
state of resonance. When the frequency of the radio waves matches with the
energy difference between the proton spin states, then the nuclei are said to be
in resonance with the electromagnetic radiation.
In order to determine to determine the resonance frequency, the energy
absorbed by nuclei is measured as the magnetic field H0 is varied. As the field
H0 is increased the processional frequency of the nucleus increases equal to the
frequency of oscillation field, transitions occurs between nuclear energy states.
The energy absorbed in this process produces a signal at the detector and this
signal is amplified and recorded as a band in the spectrum.
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[Nuclear Magnetic Resonance (NMR) Spectroscopy involves the absorption of

radio frequency radiation by atomic nuclei in an applied magnetic field. Any
atomic nucleus which possesses either odd mass, odd atomic number, or both
has spin angular momentum and a magnetic moment.
Nuclear Spin: The nuclear spin quantum number, I, determines the allowed
spin states for a nucleus: allowed spin states = 2I + 1
For hydrogen (I=), there are two spin states (2() + 1 = 2) for its nucleus:
clockwise (+) or counterclockwise (-) spin. In the absence of an external
magnetic field, these magnetic moments are randomly oriented in all
directions. If an external magnetic field is applied, the nuclear spins of the
hydrogen nuclei orient themselves either in alignment with or in opposition to
the field.
Figure1. Hydrogen nuclear spin in no external magnetic field (left) and an

applied magnetic field (right).
The two spin states for hydrogen nuclei are normally degenerate. However, in
the presence of a magnetic field, the two spin states become unequal in energy.
Those nuclei whose spin are in alignment with the external magnetic field are
lower in energy than those nuclei whose spin are in opposition to the external
field.
The energy difference between the two spin states in a magnetic field of 7.0586
Tesla is about 1.20 x 10-4 kJ/mole. Radiation with a frequency of about 300
MHz, which lies in the radio frequency region of the electromagnetic spectrum,
corresponds to this energy difference.
Figure 2 Energy differences between hydrogen nuclear spin states.
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E = 2.675 x 108 s-1T-1 * (6.626 x 10-34 / 2) * 7.0586 T
E = 1.20 x 10-4 kJ/mol
The two spin states are not equally populated; there is a small excess
population in the lower energy spin state. The nuclei in the lower spin state
can be excited into the upper spin state by absorption of energy of about 300
MHz (called resonance). This produces a signal which provides the NMR
spectrum. If the two spin states become equally populated, then no net spin
transitions are observable and no signal is produced. This situation is called
saturation. This can happen if a too powerful radio frequency pulse is used.
Hydrogen nuclei are not the only spin active nuclei. The following table
contains information about other spin active nuclei important to the organic
chemist.]
Equivalent and non-equivalent protons: A set of protons of identical

environments are known as equivalent protons while the protons with different
environment are known as non equivalent protons. The number of signals in a
PMR spectrum tells us how many kinds of protons are present in a given
molecule. Magnetically equivalent protons are also chemically equivalent.
The three methyl protons in ethyl chloride are equivalent among them but
are different from the two methylene protons. Hence ethyl chloride, CH3CH2Cl
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contains only two kinds of protons and this is confirmed by PMR spectrum of
the molecule. It gives two signals.
Examples
Br All protons equivalent, hence only on
H3C C CH3 PNR signal appears
Br
b Cl Two kinds of protons, hence
b
H3C CH CH3 two PNR signals appears
a
a b c Three kinds of protons, hence
H3C CH2 CH2 Cl
three PNR signals appears
Shielding and deshielding of protons: For determining its NMR spectrum, a
molecule is kept in a magnetic field. This causes the electrons of the molecule
to circulate and in doing so they generate secondary magnetic fields called
induced magnetic fields. The induced magnetic field may either oppose or
reinforce the applied field. If the induced field opposes the applied field the
effective field strength experiences by the proton decreases. This is known as
shielding of the proton. Compared to a necked (bare) proton, a shielded proton
needs a stronger magnetic field to produce an absorption signal or in other
words it absorbs up field.
If the induced field reinforces the applied field, the effective field strength
experienced by the proton increases. This deshielded proton naturally needs
only a smaller applied field to give a signal i.e. it absorbs downfield.
Chemical shift: The shift in the positions of PMR signals (compared with a
standard reference) resulting from the shielding and deshielding by electrons
are known as chemical shifts.
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Induced field Induced field
Applied field Applied field

H0
Applied field (Reinforce) (Opposite)

(Bare proton) Deshielding shielding
NMR signal of a bare proton
NMR signal of a deshielded proton(requires lower

applied field to flip its proton)
NMR signal of a shielded proton(requires higher

applied field to flip its proton)
The chemical shift measured in the value of (delta) which is ranges from 0 to
10 ppm or (tau) ranges from 10 to 0. A signal of tetramethylsilane is used as
reference signals for chemical shift.
Highly shielded signals

up field
Deshielded signals
downfield
10 9 8 7 6 5 3 2 1 0
4
0 1 2 3 4 5 6 7 8 9 10
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Selection of tetramethylsilane as standard in the chemical shift: To

measure the magnitudes of the chemical shifts of different kinds of protons,
there should be same signal with respect to which the measurement can be
made. For this purpose, tetramethylsilane (TMS), (CH3)4Si is used as the
reference or standard compound. It gives only one signal which serves as the
fixed reference. A small quantity of TMS is added to the sample while recording
its PMR spectrum.
The choice of TMS as reference as reference compound is based upon the
following facts.
1) TMS is having 12 equivalent protons and gives an intense single signal.
2) The electronegativity of silicon is very low (1.8) as compared to carbon (2.5).
Because of this the shielding of equivalent protons in TMS is more than that of
almost all the organic compounds. Consequently with reference to TMS signal
almost all other appear in the downfield direction.
3) TMS is chemically very inert and has a very low boiling point (300K) so that
it can be easily removed by evaporation after the spectrum has been recorded.
Factors affecting on the chemical shift: The following factors are affect on
the chemical shift.
1) Electro negativity of adjacent atoms: A proton is said to be deshielded if it
is attached with an electronegative atom or group. Greater the electronegativity
of the atom, greater is the deshielding caused to the proton. If the deshielding
is more for a proton, then its value will also be more.
Compound CH3X CH3H CH3I CH3Br CH3Cl CH3F

Element X H I Br Cl F
Electro negativity of
2.1 2.5 2.8 3.1 4.0
X
Chemical Shift () 0.23 2.16 2.68 3.05 4.26
Consider the following compounds:
28
b a b a
i) H3C CH2 F ii) H3C CH2 Cl
Two signals are expected for each of the two compounds. Deshielding for
protons a in compound (i) is more than that for similar protons in compound
(ii)
As the distance from the electronegative atom increases, the deshielding effect
due to it diminishes. Protons b is comparatively less deshielded and hence will
resonate at comparatively lower value of .
2) Types of hybridization: In hydrocarbon compounds the protons in SP3
hybridized carbon atom is more desheilded than SP2 hybridized carbon atom
which is more shielded than SP hybridized carbon atom. This is due to induced
magnetic field oppositely increases from SP3 to SP2 and SP2 to SP hybridized
carbon atom attached to the proton.
sp3 Hydrogens: Hydrogens attached to sp3 hybridized carbon atoms resonate

between 0 - 2 ppm.
sp2 Hydrogens: Hydrogens attached to sp2 hybridized carbon atoms resonate

farther downfield than for normal aliphatic protons. The shift from TMS is
dependent on the type of sp2 hybridized carbon atom
Vinylic Hydrogens: Hydrogens attached to carbon-carbon double bonds
resonate between 4.5 - 7 ppm. The sp2 hybridized carbon atom of the double
bond has increased s-character, and is therefore more electronegative than a
sp3 hybridized carbon atom.
Aromatic Hydrogens: Aromatic hydrogens resonate between 7 - 8 ppm.
Aldehyde Hydrogens: Aldehyde protons resonate between 9 - 10 ppm. This
further downfield shift is due to the additional effect of the electron
withdrawing oxygen atom nearby.
sp Hydrogens: Acetylenic hydrogens resonate between 2 - 3 ppm due to the
anisotropy of the carbon-carbon triple bond.
29
3) Magnetic induction in a pi system (Anisotropic effect): All groups in a

molecule with electrons will have an effect on the local magnetic field due to
the induced circulation of these electrons.
For example, in aromatic Rings the electrons in an aromatic ring are

induced to circulate around the ring in response to an applied magnetic field.
This "ring current" generates a local magnetic field which opposes the applied
magnetic field. However, on the periphery of the ring, the flux lines are in the
direction of the applied magnetic field. Consequently, protons attached to the
aromatic ring "feel" a larger magnetic field than protons elsewhere in the
molecule. Aromatic ring protons will therefore resonate at higher frequency and
exhibit a downfield shift (7 - 8 ppm).
In acetylenic Hydrogens the electrons in a triple bond circulate around

the bond axis to produce a magnetic field directly opposing the applied
magnetic field. The acetylenic hydrogen is shielded by this induced field, and
will therefore resonate at lower frequency (2 -3 pmm).
30
Spin spin splitting: A single signal is split into number of peaks due to
shielding of a given set of equivalent protons by protons of adjacent carbon
atoms called spin-spin splitting or multiplets.
Ex. Spin - spin splitting in ethanol, TMS

H3C CH2 OH Triplet
a b c
singlet Quartet a
b
c
10 9 8 7 6 5 4 3 1 0
2
To understand spin spin splitting in ethanol, first consider, the influence of

methylene protons on the methyl protons. Each proton is the methylene group
may have its magnetic moment liked up with or against the applied field. This
results in four possible combinations.
(a) (b) (c) (d)
Combinations (b) and (c) will have the same shielding effect on the adjacent
methyl group. Hence there are three different shielding combinations and the
methyl proton signal is split into a triplet. At any given moment, 25% of
methylene protons will be in combination (a), 25% in (d) and 50% in (b) and (c).
Thus the ratio of the areas of the triplet formed will be 1:2:1.
Applying the same condition to the methyl protons on the methylene protons,
there are four sets of shielding combinations.
(i) (iv)
(ii) (iii)
Thus the signal of methylene proton is split into a quartet, the ratio of the
areas being 1:3:3:1
31
In general, if a proton has n number of neighboring non equivalent protons,

its signal is split into (n + 1) peaks. The number of peaks into which a
particular signal is split is called its multiplicity.
a b
Ex. H3C CH Cl 2 NMR signals obsreved
Cl
There are two kinds of protons and hence two signals are formed. The signal
produced by CH3 (a) proton is split into a doublet by the neighboring proton
(b).Similarly the signal produced by proton b is split into a quartet ( n + 1 = 3
+ 1 = 4) by three methyl proton.
Spin spin coupling: The interaction between the nuclei of chemically non-
equivalent neighboring protons is called as spin-spin coupling. The interaction
takes place trough intervening covalent bond. Therefore the strength of the
interaction depends on the number of intervening bonds. Greater the number
of intervening bonds, lesser the interaction.
Coupling constant: the magnitude of interaction or coupling is known as
coupling constant. It is denoted by a letter J.
OR
The distance between the centers of two adjacent peaks in a particular
multiplet is shown by the value of J and is called coupling constant.
Table shows NMR signals of some general compounds:
32
1H MR Spectra of Methane: In methane (CH4), all four hydrogens having same

environment. Hence it gives single signal at 0.7 value in ppm.
TMS
Singlet
1HNMR of CH4
10 9 8 7 6 5 4 3 2 1 0

33
1H MR Spectra of Methyl chloride: In CH3Cl, all three hydrogens are in same

environment. Hence it expected to gives single peak at 0.7 ppm of but a
chloro (-Cl) electronegative group present hence this signal is shifted to
downfield (deshielded) and appears at 3.1 .
TMS
Singlet
1HNMR of CH3Cl
10 9 8 7 6 5 4 3 2 1 0

1H MR Spectra of Dichloromethane (CH2Cl2): In CH2Cl2, all two hydrogens

are in same environment. Hence it expected to gives single peak at 0.7 ppm of
but two chloro (-Cl) electronegative groups present hence this signal is shifted
to downfield (deshielded) and appears at 3.8 .
TMS
1HNMR of CH2Cl2
Singlet
10 9 8 7 6 5 4 3 2 1 0

34
1H MR Spectra of Trichloromethane (CHCl3): In CHCl3, hydrogen is in same

environment. Hence it expected to gives single peak at 0.7 ppm of but three
chloro (-Cl) electronegative groups present hence this signal is shifted to
downfield (deshielded) and appears at 4 .
TMS
1HNMR of CHCl3
Singlet
10 9 8 7 6 5 4 3 2 1 0

Spin- spin coupling in Dichloroacetaldehyde (Cl2CHCHO):
2 1 TMS
1HNMR of Cl2CHCHO
Doublet Doublet
Cl2CH- -CHO
J J
10 9 8 7 6 5 4 3 2 1 0

35
Dichloroacetaldehyde, Cl2CHCHO, has two inequivalent H atoms, H1 and H2.

We expect to see two resonances, one at around 9.8 ppm and one around
5.5 ppm. (The H2 resonance is so far downfield because there are two Cl atoms
attached to C2.) One H atom contributes to one resonance, and one H atom
contributes to the other resonance, so we expect them to integrate to a 1:1
ratio. The 1H resonating at 9.8 ppm, H1, has one magnetically active neighbor,
H2. These atoms are separated by three bonds, so we expect to see a coupling
constant. The resonance at 9.8 ppm is split into two peaks of equal intensity,
a doublet. Likewise, H2 has one magnetically active neighbor, so its resonance
is split into a doublet too. The spectrum consists of two doublets. There is one
H1- H2 coupling constant, so the J values for one resonance, obtained by
Measuring the distance between the peaks in ppm and multiplying by the
Spectrometer frequency is the same as the J value for the other resonance.
Spin- spin coupling in 1,1, 2- trichloroethane: Consider the spectrum for
1,1,2-trichloroethane. In this and in many spectra to follow, we show
enlargements of individual signals so that the signal splitting patterns are
recognizable.
The signal at 3.96 ppm, corresponding to the two Ha protons, is split into two
subpeaks of equal height (and area) this is referred to as a doublet. The Hb
signal at 5.76 ppm, on the other hand, is split into three sub-peaks, with the
middle peak higher than the two outside peaks - if we were to integrate each
36
subpeak, we would see that the area under the middle peak is twice that of
each of the outside peaks. This is called a triplet.
The source of signal splitting is a phenomenon called spin-spin coupling, a

term that describes the magnetic interactions between neighboring, non-
equivalent NMR-active nuclei. In our 1,1,2 trichloroethane example, the Ha and
Hb protons are spin-coupled to each other. Here's how it works, looking first at
the Ha signal: in addition to being shielded by nearby valence electrons, each of
the Ha protons is also influenced by the small magnetic field generated by Hb
next door (remember, each spinning proton is like a tiny magnet). The magnetic
moment of Hb will be aligned with B0 in (slightly more than) half of the
molecules in the sample, while in the remaining half of the molecules it will be
opposed to B0. The Beff felt by Ha is a slightly weaker if Hb is aligned against
B0, or slightly stronger if Hb is aligned with B0. In other words, in half of the
molecules Ha is shielded by Hb (thus the NMR signal is shifted slightly upfield)
and in the other half Ha is deshielded by Hb (and the NMR signal shifted slightly
downfield). What would otherwise be a single Ha peak has been split into two
sub-peaks (a doublet), one upfield and one downfield of the original signal.
These ideas an be illustrated by a splitting diagram, as shown below.
Now, let's think about the Hb signal. The magnetic environment experienced by
Hb is influenced by the fields of both neighboring Ha protons, which we will call
Ha1 and Ha2. There are four possibilities here, each of which is equally
probable. First, the magnetic fields of both Ha1 and Ha2 could be aligned with
37
B0, which would deshield Hb, shifting its NMR signal slightly downfield.
Second, both the Ha1 and Ha2 magnetic fields could be aligned opposed to B0,
which would shield Hb, shifting its resonance signal slightly upfield. Third and
fourth, Ha1 could be with B0 and Ha2 opposed, or Ha1 opposed to B0 and Ha2
with B0. In each of the last two cases, the shielding effect of one Ha proton
would cancel the deshielding effect of the other, and the chemical shift of Hb
would be unchanged.
So in the end, the signal for Hb is a triplet, with the middle peak twice as large
as the two outer peaks because there are two ways that Ha1 and Ha2 can cancel
each other out.
Spin spin coupling in chloroethane:
2 1 TMS
1HNMR of ClCH2CH3 quartet
ClCH2-
triplet
-CH3
J
J
10 9 8 7 6 5 4 3 2 1 0

38
Chloroethane, ClCH2CH3, has two inequivalent H atoms, H1 and H2. We

expect to see two resonances, one at around 1.5 ppm and another at around
3.6 ppm. The field for the identical protons on C1 is split into four (ratio
1:3:3:1) by the three protons on C2:
, ,
, ,
The three protons on C2 are split into a triplet (1:2:1) by the two protons on C1.
The quadruplet appears down field due to the proximity of the chlorine atom.
Measuring the distance between the centre of two peaks gives the coupling
constant.
Applications of NMR spectroscopy including identification of simple
organic molecules:
1H MR Spectra of 1-chloroethane:
The field for the identical protons on

C1 is split into four (ratio 1:3:3:1) by
the three protons on C2:
, ,
, ,
The three protons on C2 are split into

a triplet (1:2:1) by the two protons on
C1.
The quadruplet appears down field

due to the proximity of the chlorine
atom.
1H MR spectra 1-chloropropane: CH3-CH2-CH2-Cl
39
Triplets (1:2:1) arise for the protons

on C1 and C3 which both have the two
protons on C2 as neighbors.
The two protons on C2 have 5 (=3+2)

nearest neighbor protons which
produces a 6-fold split (1:5:10:10:5:1).
In fact, this is really a 4 x 3 = 12-fold
split but there is considerable overlap
it appears as only 6 peaks.
1H MR Spectra of 2, 2-dichloropropane:
Lets look at some specific examples. Dichloroacetaldehyde, Cl2CHCHO, has
two inequivalent H atoms, H1 and H2. We expect to see two resonances, one
at around 10.5 ppm and one around 5.5 ppm. (The H2 resonance is so far
downfield because there are two Cl atoms attached to C2.) One H atom
contributes to one resonance, and one H atom contributes to the other
resonance, so we expect them to integrate to a 1:1 ratio. The 1H resonating
at 10 ppm, H1, has one magnetically active neighbor, H2. These atoms are
separated by three bonds, so we expect to see a coupling constant. The
resonance at 10 ppm is split into two peaks of equal intensity, a doublet.
Likewise, H2 has one magnetically active neighbor, so its resonance is split
into a doublet too. The spectrum consists of two doublets. There is one H1-
H2 coupling constant, so the J values for one resonance, obtained by
measuring the distance between the peaks in ppm and multiplying by the
spectrometer frequency, is the same as the J value for the other resonance.
A single peak is observed for this

compound with its six chemically
equivalent protons.
Since they are not on adjacent carbons,

the fields are not perturbed so no
splitting is observed.
NB. Long range coupling can be found

in some organics.
1H MR Spectra Methanol: CH3-O-H
40
No splitting since only protons bonded

to adjacent carbons appears to cause
coupling.
Hence, there are two singlets.

Similarly, functional group protons in -
COOH and -NH- cause no splitting but -
CHO can produce a doublet.
41
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
UNIT IV
Aliphatic Hydrocarbons
9 hours: Max. Marks: 18 -20
Syllabus:
Alkanes: Sources, Nomenclature of branched chain alkanes, preparation of symmetrical and

unsymmetrical alkanes- Corey- House reaction and Wurtz reaction - their merits and
demerits. Conformational analysis of n-butane - Sawhorse and Newman projection formulae
to be used -Energy profile diagram.
Cycloalkanes: Nomenclature. Method of formation. Explanation for stability based on heat
of hydrogenation data, Baeyers strain theory and its limitation, Sachse - Mohr theory of
strain-less rings; cyclopropane ring - banana bonds.
Alkenes: Preparation of alkenes by Wittig reaction-stereoselectivity. Addition of HX to
unsymmetrical alkene - Markownikovs rule and Antimarkownikovs rule with mechanism.
Reactions: Hydroboration- oxidation, reduction, oxymercuration demercuration
epoxidation. Mechanism of oxidation with KMnO4 and OsO4.Ozonolysis- mechanism and
importance.
Dienes: Classification- isolated, conjugated, cumulated. Structure of allene and butadiene.1,2
addition and 1,4 addition reactions. Diels Alder reaction-1,3-butadiene with maleic
anhydride.
Alkynes: Methods of preparation - Dehydrohalogenation of vicinal and geminal dihalides;
and higher alkynes from terminal alkynes. Reactions - metal ammonia reduction
significance. Oxidation with KMnO4, acidic nature of terminal alkynes.
Aliphatic hydrocarbons: A branch of organic chemistry which deals with study of open
chain compounds containing carbon and hydrogen as elements called aliphatic hydrocarbons.
Classifications of aliphatic hydrocarbons: They are classified as
1) Alkanes 2) Cycloalkanes 3) Alkenes 4) Dienes 5) Alkynes.
1) ALKANES: Alkanes are the simplest organic compounds made of carbon and hydrogen
only. They have the general formula CnH2n + 2, where, n= 1, 2, 3, etc. the first three members
of this class can be represented as
H H H H H H
H C H H C C H H C C C H
H H H H H
H
Methane Propane
Ethane
The carbon atoms in their molecules are bonded to each other by single covalent bonds. Each
carbon is again bonded to enough hydrogen atoms to give maximum covalence of 4. Since
the carbon skeleton of alkanes is fully saturated with hydrogens. They are also called
saturated hydrocarbons.
Alkanes contain strong C-C and C-H covalent bonds. Therefore, this class of hydrocarbons is
relatively chemically inert. Hence they are sometimes referred to as paraffins.
Page 1 of 35
Sources of alkanes: Alkanes are occurred in
1) Natural gas contains about 80% methane and 10% ethane, the remaining 10% being a
mixture of higher members.
2) Petroleum is the source of C5 C20 hydrocarbons.
3) Plant waxes also contain saturated hydrocarbons having odd number of carbon atoms (C27
to C37). Bee wax contains C27H56 and C31H64.
Nomenclature of alkanes: There are two system of naming alkanes:
1) Common system: The first four members of the series are called by their common names:
methane, ethane, propane and butane. The names of larger alkanes are derived from the
Greek prefixes that the number of carbon atoms in the molecule. Thus, pentane has five
carbons, hexane has six, and so on.
No. of carbon Name Molecular Structure of the normal isomer

atoms formula
1 Methane CH4 CH4
2 Ethane C2H6 CH3CH3
3 Propane C3H8 CH3CH2CH3
4 Butane C4H10 CH3CH2CH2CH3
5 Pentane C5H12 CH3CH2CH2CH2CH3
6 Hexane C6H14 CH3CH2CH2CH2CH2CH3
7 Heptane C7H16 CH3CH2CH2CH2CH2CH2CH3
8 Octane C8H18 CH3CH2CH2CH2CH2CH2CH2CH3
9 Nonane C9H20 CH3CH2CH2CH2CH2CH2CH2CH2CH3
10 Decane C10H22 CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
In the common system all isomeric alkanes have the same parent name. For
examples, two isomeric C4H10 alkanes are known as butanes. The names of various isomers
are distinguished by prefixes. The prefix indicates the type of branching present in the
molecule.
1) Prefix n- is used for those alkanes in which all carbons are in one continuous chain. The
prefix n stands for normal.
H3C CH2 CH2 CH3 H3C CH2 CH2 CH2 CH3

n - Butane n - Pentane
2) Prefix iso is used for those alkanes which have a methyl groups attached to the second
last carbon atom of the continuous chain.
CH3 CH3
H3C CH CH3 H3C CH CH2 CH3
Isobutane Isopentane
Page 2 of 35
3) Prefix neo- is used for those alkanes which have two methyl groups attached to the second
last carbon atom of the continuous chain.
CH3
H3C C CH2 CH3
CH3
Neohexane
The structural formulas of alkanes contain four types of carbon atoms:
1) A carbon atom attached to one other (or no other) carbon is called primary carbon (10
carbon).
2) A carbon atom attached to two other carbon atoms is called secondary carbon (20 carbon).
3) A carbon atom attached to three other carbon atoms is called tertiary carbon (30 carbon).
4) A carbon atom attached to four other carbon atoms is called quaternary carbon (40 carbon).
Hydrogen atoms attached to 10 , 20, 30 carbon atoms are often referred to as primary,
secondary and tertiary hydrogen atoms.
CH3 CH3
H3C C CH CH2 CH3
0
Primary carbon (1 )
CH3 0
Secondary carbon (2 )
0
Tertiary carbon (3 )
0
Quarternary carbon (4 )
Alkyl groups: An alkyl group is formed by removing one hydrogen from an alkane. They are
named simply by dropping ane from the name of the corresponding alkane and replacing it
by yl (alkane ane + yl = alkyl).
Parent alkane Structure Alkyl group Name of alkyl group

Methane CH4 CH3- methyl
Ethane CH3CH3 CH3CH2 - ethyl
Propane CH3CH2CH3 CH3CH2CH2 - propyl
n -Butane CH3CH2CH2CH3 CH3CH2CH2CH2- n-butyl
Isobutane (CH3)2CHCH3 (CH3)2CHCH2 - isobutyl
II) IUPAC system: The IUPAC system is much the same for all families of organic
compounds. The steps for alkanes are as follows.
Prefix Parent Suffix
Indicates location Indicates the family

of substituents Indicates number of the molecules
of carbons
Page 3 of 35
1) Name the longest chain: The longest continuous carbon chain is chosen as the basic for
the name and it written in horizontal fashion.
H3C CH2 CH CH3 The longest continuous chain has fou

carbon atoms, Thus, the compound
CH3 is named as a butane.
2) Number the longest chain: The carbon atoms in the longest chain are numbered. The
numbering is started from that end which will give numbers having the lowest value to
carbons carrying substituents.
4 3 2 1 1 2 3 4
H3C CH2 CH CH3 and not H3C CH2 CH CH3
CH3 CH3
3) Locate and name the constituents: Each substituent is named, and the position of each
substituent is indicated by the number of the carbon atom to which it is attached.
4 3 2 1 The attached group is located on carbo

H3C CH2 CH CH3
2 of the chain and it is a methyl group
CH3
4) Combine the longest chain and substituents into the name: The position and the name
of the substituent are added to the name of the longest chain and written as one word.
4 3 2 1
H3C CH2 CH CH3 2 - Methylbutane
CH3
2- Methyl Butane
Position of Attached Longest
alkyl group alkyl group Chain
Additional steps are needed when more than one substituent is attached to the longest chain.
5) Indicate the number and position of substituents: If the same substituent is present two
or more times in the molecule, the number of this substituent is indicated by a prefix di-, tri-,
tetra-, penta-, etc., and the location of each is indicated by a separate number. These position
numbers, separated by commas, are put just before the name of the substituent, with hyphen
before and after the numbers when necessary.
1 CH3
2 3 4 5 1 2 3 4 5
H3C CH CH2 CH CH3 H3C CH2 C CH2 CH3
CH3 CH3 CH3
2,4 - Dimethylpentane 3,3 - Dimethylpentane
Preparation of symmetrical alkanes (Wurtz reaction): Higher alkanes are produced by

heating alkyl halides with sodium metal in dry ether solution. Two molecules of the alkyl
Page 4 of 35
halide loss their halogen atoms as NaX. The net result is the joining of two alkyl groups to a
symmetrical alkanes (R-R type) having an even number of carbon atoms.
Dry ether
R - X + 2Na + X - R' R - R' + 2NaX
Alkyl halide Alkane
Where, R = R' = alkyl group

Dry ether
Mechanism: R - X + 2Na R - Na + NaX
Dry ether
R - Na + R' - X R - R' + NaX
Dry ether
R - X + 2Na + X - R' R - R' + 2NaX
R' for unsymmetric alkanes.
Where, R = R' for symmetric alkanes and R
Examples: 1) R = R = - CH 3 and X = - Cl
Dry ether
CH 3 - Cl + 2Na + CH3 - Cl CH 3 - CH 3 + 2NaX
Methyl chloride Ethane
2) R = R' = CH3 - CH 2 - and X = - Br

Dry ether
CH 3 - CH 2 - Br + 2NaX + CH3 - CH 2 - Br CH 3 - CH 2 - CH 2 - CH 2 - CH 3 + 2NaX
Ethyl bromide Ethyl bromide n - butane
Merits of Wurtz reaction:
1) This method is satisfactorily explained to prepare symmetric alkanes in good yield.
2) This method is satisfactorily explained to prepare higher alkanes from the lower alkyl
halides.
Demerits of Wurtz reaction:
1) This method fails to prepare unsymmetrical alkanes because it very difficult to separate.
2) This method fails to prepare alkanes from alcohol or from fatty acids.
3) This reaction is fails to prepare methane.
Preparation of unsymmetrical alkanes by Corey House method: An alkyl halide is first

converted to lithium dialkyl copper, LiR2Cu. This is then treated with an alkyl halide to give
an alkane.
Page 5 of 35
2Li CuI
R-X R - Li (R) 2CuLi
- LiX
Alkyl halide Ethyl lithium Lithium dialkyl copper
(R) 2CuLi + R' - X R - R' + R -Cu + LiX

Alkyl halide Alkane Alkyl copper
Where, R R' = Alkyl group
Example 1) R = CH3 CH2 - , R' = - CH3 , X = Br
2Li CuI
CH 3CH 2Br CH 3CH 2Li (CH 3CH 2)2CuLi + LiI
- LiBr
Ethyl bromide Ethyl lithium Lithium diethyl copper
(CH 3CH 2)2CuLi + CH3Br CH 3CH 2CH 3 + CH3CH 2Cu + LiBr

Methyl bromide Propane Ethyl cuperate
Example 2) R = CH3CH 2CH 2 - , R' = CH3CH 2 - , X = Br
CH 3CH 2CH 2Br 2Li CuI

CH 3CH 2CH 2Li (CH 3CH 2CH 2)2CuLi + LiI
- LiBr
Propyl bromide Propyl lithium Lithium dipropyl copper
(CH 3CH 2CH 2)2CuLi + CH3CH 2Br CH 3CH 2CH 2CH 2CH 3 + CH3CH 2CH 2Cu + LiBr
Lithium dipropyl copperEthyl bromide n - Pentane Propyl cuperate
Merit of Corey House reaction: This method is satisfactorily explained the preparation of
unsymmetrical alkanes.
Conformations of alkanes: The different spatial arrangements of a molecule that can be

obtained by free rotation around carbon carbon single bonds are called conformations.
Sawhorse representation formulae of alkanes: In sawhorse projection, the carbon atom at

the left of the structure is considered to be close to the observer than in carbon at the right.
H
CH 3 CH 3
Example,
H
H H H
H H H
H H H
H H
H
H CH 3
Ethane
Propane n - Butane
Staggered conformations
Page 6 of 35
H
CH 3 CH 3
H
H H H H
H H CH 3 H
H
H H
H H
H
Ethane
Propane n - Butane
Eclipsed conformations
Newman projection formulae of alkanes: In Newman projection formulae, one is viewing

the C C bond end on along the axis of connection. The front carbon atom is represented by
the intersection of bonds from it, while the rear carbon appears as a circle.
Example, H
CH 3 CH3
H H H H H H
H H
H H H H
H
H CH 3
Ethane Propane
n - Butane
Staggered conformations
H H H
H H H H
H H
H CH 3 H
H H
H3C
H H CH 3
Ethane Propane
n - Butane
Eclipsed conformations
Conformations analysis of n butane: n Butane is a somewhat complex molecule from

the standpoint of conformation because there are three carbon carbon single bonds (one
central and two terminal) around which rotation can take place. If we consider rotation about
the central carbon carbon bond C2 C3, the situation is quite similar to that in the case of
ethane, except that n butane molecule has more than one staggered and eclipsed
conformations. Staggering or eclipsing in these conformations may be complete or partial as
shown below.
Page 7 of 35
CH 3 H
H H H H
H H H
CH 3
H H CH 3
H
H CH 3
CH 3 CH 3
Anti form (I) Eclipsed form (II) Gauche form (III)
H
H H H H CH 3
H H
H H
H
CH 3 H
H3C H
CH 3 CH 3
CH 3
Fully eclipsed form (IV) Gauche form (V) Eclipsed form (VI)
The completely staggered conformation (I) called the anti form shows the methyl groups
as far apart as possible. Assuming that the angle of rotation about the central C2 C3 bond is
zero for conformation I, if we rotate one of the C2 or C3 carbon atoms through an angle of
600, the eclipsed form (II) appears. In conformation (II) the methyl group attached to one
carbon is at the back of hydrogen, rather than the methyl group attached to the other carbon.
Rotation by another 600 leads to a staggered conformation (III) also called gauche form, in
which the two methyl groups are only 600 apart. Further rotation by 600 gives rise to the fully
eclipsed conformation (IV). On further rotation by 600 the gauche form (V) appears in which
the two methyl groups are again 600 apart. Still further rotation by 600 leads to the eclipsed
form (VI). If we rotate (VI) by another 600 thereby completing a rotation of 3600, we return
to the anti form (I).
Energy profile diagram: The relative stabilities of conformations of n butane could be

seen in the following figure.
5 (IV)
Potential energy in kcal
4
(II) (VI)
3
4.5 - 5 kcal
2
3.5kcal 3.5kcal
(III) (V)
1
0.9kcal 0.9kcal
0 ............................................................................................................................................
(I) (I)
0 0 0 0 0 0 0
0 60 120 180 240 300 360
Angle of rotation
Page 8 of 35
The above figure depicts the energy changes during rotation about C2 C3 bond in n
butane. It will be observed that the anti conformation (I) would be the most, and the fully
eclipsed conformation (IV) the least stable conformation of n butane. The gauche
conformation (III) and (V) would be slightly less stable than the anti conformation (I) and the
eclipsed conformation (II) and (VI) would be slightly more stable than the fully eclipsed
conformation (IV).
2) Cycloalkanes: Cycloalkanes or cycloparaffins are saturated hydrocarbons in which the

carbon atoms are joined by single covalent bonds to form a ring. They are also called
alicyclic compounds. The prefix ali is added because of their similarity to aliphatic
compounds. The unsubstituted cycloalkanes from a homologous series with the general
formula CnH2n. Where n = 3, 4, 5, 6, etc.
Examples: cyclopropane, cyclobutane, cyclohexane, etc.
Nomenclature: The IUPAC rules for naming cycloalkanes are follows:
Rule 1) Name of an unsubstituted cycloalkane is obtained by attaching the prefix cyclo to

the name of the corresponding normal alkane having the same number of carbon atoms as in
the ring.
CH2 H2C CH2
H2C CH2 , H2C CH2

Cyclopropane Cyclobutane
CH2
CH2
H2C CH2
H2C CH2
H2C CH2
CH2 CH2
CH2
Cyclopentane Cyclohexane
Rule 2) Substituents on the ring are named and their positions are indicated by numbers. The
ring is numbered so that carbons bearing the substituents will have the lowest numbers. If
possible indicate stereochemistry.
CH2 CH3 H3C CH3

1 H CH3
2 CH2CH2 CH3
H H CH3 H
1 -Ethyl -2 - propylcyclohexane
Cis 1,2 - dimethyl cyclopropane
(Follow alphabetic order) Trans 1,2 - dimethylcycopropane
Rule 3) Naming alkyl substituted cycloalkanes. Count the number of carbon atoms in the ring
and also in the largest alkyl substituent.
a) If the number of carbon atoms in the ring is equal to or greater than the number in the
largest substituent, the compound is named as alkyl substituted cycloalkanes (Example -1). If
Page 9 of 35
the number of carbon atoms in the ring is less than the number of carbon atoms in the
substituent. It is named as a cycloalkyl substituted alkane (Example -2).
2 1
CH3
CH2 CH2 CH3
CH CH2 CH2 CH3
1 2 3 4 5
CH3
2 - cyclopropylpentane
1 - methyl 2 - propylcyclobutane
Example - 2
Example - 1
b) If there is a tie between the number of carbons on the cycloalkane part of the molecule and
the acyclic alkane part, choose the cycloalkane as the parent (main) chain.
1 2 3 4 5
CH2 CH2 CH2 CH3 CH2 CH2 CH2 CH2 CH3
Butylcyclobutane 1 - cyclobutylpentane
Methods of preparation of cycloalkanes:
1) From dihalides (Freunds method): Terminal dihalides when treated with sodium or zinc
to from cycloalkanes. This reaction is an extension of Wurtz reaction and is useful for the
preparation of 3- to 6 membered rings.
CH2 X
(CH 2)n
+ 2Na + 2NaCl
(CH 2)n
CH2 X
Dihalide alkane Cycloalkane
Where, n = 1,2,3,4,etc.
CH2 Cl
Examples:1) n = 1, H2C
+ 2Na + 2NaCl
X = - Cl
CH2 Cl
Cyclopropane
1,3 - Dichloropropane
2) n = 3, CH2 CH2 Br + 2NaCl

H2C + 2Na
X = - Br
CH2 CH2 Br
Cyclopentane
1,5 - Dibromopentane
2) From calcium salts of dicarboxylic acids: When the calcium or barium salts of
dicarboxylic acids are heated, cyclic ketones are formed. The cyclic ketones can be readily
converted into the corresponding cycloalkanes by Clemmensen reduction.
Page 10 of 35
O
O
CH2 C Clemmensen reduction
H2C O
Zn or Hg
Ca
- CaCO 3 HCl
H2C CH2 C O
cyclopentane
cyclopentanone
O
Calcium adipate
3) From esters of dicarboxylic acids (Dieckmann reduction):

O
H2C CH2 C OC2H5 +

Na H2O/H
O O
- C 2H5OH
H2C CH2
COOC2H5 COOH
COOC2H5
ketoester ketoacid
Diethyl adipate
Clemenmensen reduction

O
- CO 2 Zn or Hg / HCl
Cyclopentane
pentanone
4) From aromatic hydrocarbon:
Ni,
+ 3H2
Pressure
Benzene Cyclohexane
Stability of cycloalkanes:
1) Based on the heat of hydrogenation data:
Cycloalkane up to cyclopentane adds hydrogen in presence of nickel at the specific

temperature.
Page 11 of 35
Ni
+ H2 H3C CH2 CH3
0
80 C Propane
Cyclopropane
Ni
+ H2 H3C CH2 CH2 CH3
0
120 C n - Butane
Cyclobutane
Ni
+ H2 H3C CH2 CH2 CH2 CH3
0
300 C n - Pentane
Cyclopentane
Higher cycloalkanes are not affected by hydrogenation reaction in presence of nickel.
In the above hydrogenation reactions breaking of one of the C C bond in

cyclopropane requires small temperature, in cyclobutane requires more temperature , in
cycopentane requires still more temperature and in higher cycloalkanes i.e. in cyclohexane,
cycloheptane, etc. no bond is break. This indicates that cyclopropane is least stable than the
cyclobutane, which less stable than cyclopentane. Therefore stability of cycloalkanes in the
following order:
Cyclobutane Cyclopentane Cyclohexane

Cyclopropane
Stability increases
Baeyers strain theory of stability of cycloalkanes: Adolf Baeyer proposed a theory to

explain the relative stability of the first few cycloalkanes. He based his theory on the fact that
the normal angle between any pair of bonds of a carbon atom is 109028. Baeyer postulated
that any deviation of bond angles from the normal tetrahedral value would impose a condition
of internal strain on the ring. He also assumed that all cycloalkanes were planar and thus
calculated the angle through which each of the valence bonds was deflected from the normal
direction in the formation of the various rings. This he called angle strain. This determined
the stability of the ring.
Page 12 of 35
C
0 0
60 24 44'
0
109 28'
C C
In cyclopropane, the three carbon atoms occupy the corners of an equilateral triangle, thus
cyclopropane has C C-C bond angle of 600. This implies that the normal tetrahedral angle of
1090 28 between any two bonds is compressed to 600, and that each of the two bonds
involved is pulled in by (1090 28 - 600) = 240 44. The value 240 44 then represents the
angle strain or the deviation through which each bond bends from the normal tetrahedral
direction.
The angle strain for other cycloalkanes can be calculated in the same way. The values are
given in table below. Whether the angle of strain is positive or negative, its magnitude
determines the extent of strain in the ring.
No. of carbon Structure C C- C bond angle Angle of strain

atoms in the ring
3 (109028 - 600) = 240 44
600
4 (109028 - 900) = 90 44
900
5 (109028 - 1080) = 00 44
0
108
6 (109028 - 1200) = -50 16

1200
7 (109028 - 128035) = -90 46

0
128 6
8 (109028 - 1350) = -120 47

1350
Merits (supports) of Baeyers strain theory:
Page 13 of 35
1) This theory satisfactorily explains the stability of small ring cycloalkanes like
cyclopropane, cyclobutane and cyclopentane.
2) This theory satisfactorily calculates the enthalpy of combustion of cycloalkanes per CH2
per group.
Demerits of Baeyers strain theory:
1) This theory fails to explain the stability of cyclohexane and other higher membered of
cycloalkane.
2) This theory fails to explain why the ethylenic bond formed readily instead of formation of
cycloalkane.
Sache Mohr theory of strainless cycloalkanes: In order to account for the stability of
cyclohexane and higher members, Sache Mohr proposed that such rings can become free
from strain if the all ring carbons are not forced into one plane, as was assumed by Baeyer. If
the ring assumed a folded or puckered condition, the normal tetrahedral angles of 109028 are
retained and as a result, the strain within the ring is relieved. As shown in figure.
Fol ded or puckered form of cyclohexane
For example, cyclohexane can exist in two non planar puckered conformations both of
which are completely free from strain. These are called the chair form and the Boat form
because of their shape. Such non planar strain free rings in which the ring carbons can
have normal tetrahedral angles are also possible for higher cycloalkanes.
Examination of the chair form of cyclohexane reveals that the hydrogen atoms can be
divided into two categories. Six of the bonds to hydrogen atoms point straight up or down
almost perpendicular to the plane of the molecule. These are called axial hydrogens. The
other six hydrogens lie slightly above or slightly below the plane of the cyclohexane ring, and
are called equatorial hydrogens.
Page 14 of 35
Ha Ha
Ha Ha
He He 1 6
He He He
He He
Ha
Ha
Ha Ha
He He He
He He
Ha Ha
Ha Ha
Boat - form
Chair - form
Relative stability of cyclohexane: Chair form of cyclohexane is more stable than boat
form due to following reason.
1) Under ordinary condition, cyclohexane molecule will mostly exist in chair form.
2) In boat form of cyclohexane, two axial hydrogens present at C -1 and C -2 are like flag
pole and they are very close to each other and there is repulsion between them. Hence this
acquires more energy and it is unstable.
Banana bonds in cyclopropane ring: In cyclopropane, the C C bonds are neither sigma
bond (maximum SP3 SP3 orbitals overlapping) nor pi bond (minimum SP3 SP3 orbitals
overlapping) but they are intermediate of these two. This type of bond is called banana bond
or bent bond. In cyclopropane, bond angle is small this is due overlap of the sp3 orbitals of
the carbon is less than the overlap of the sp3 orbitals of carbons in normal propane.
Maximum overlap
H
Strong bond H
H
Minimum overlap
H Weak bond
H H
C 0
109 28'
H
H H
0
H 60
H H H
H
Bonding in propane Bonding in cyclopropane

(Banana bond)
3) ALKENES: Alkenes are hydrocarbons that contain a carbon carbon double bond (C=C)
in their molecules. They have the general formula CnH2n (n = 2, 3, 4, etc.). Alkenes are
commonly known as olefins (Latin, Oleum = oil; fiacre = to make) because the lower
members form oily products on treatment with chlorine or bromine.
Examples:
Page 15 of 35
Value n in CnH2n Structure Name
2 CH2 = CH2 Ethylene (ethane)
3 CH3CH2 = CH2 Propylene (propene)
4 CH3CH2CH2 = CH2 1 Butene

CH3CH = CH CH3 2 - Butene
Preparation of alkenes by Wittig reaction: Wittig reaction involves the preparation of
olefins by the interaction of aldehydes or ketones (aliphatic or aromatic) with
triphenylphosphine -alkylidines.
R1 R1
C O + H2C = P(C6H5)3 C CH 2 + (C 6H5)3P = O
R2 Triphenylphosphine oxid
R2 Triphenylphosphine- methylene
Aldehydes Alkenes
(or ketones)
Where, R1 = R2 = H or alkyl group
For examples 1) When R1 = R2 =H

H
C O + H2C = P(C6H5)3 H2C CH 2 + (C 6H5)3P = O
Ethylene (ethene) Triphenylphosphine oxide
H Triphenylphosphine- methylene
Formaldehyde
2) When R1 = - CH3 R2 =H
H3C
C O + H2C = P(C6H5)3 H3C CH CH 2 + (C 6H5)3P = O
Propene Triphenylphosphine oxid
H Triphenylphosphine- methylene
Acetaldehyde
3) When R1 = - CH3 R2 = - CH3
H3C
H3C
C O + H2C = P(C6H5)3 H3C C CH2 + (C 6H5)3P = O
2 - methyl 1 - propene Triphenylphosphine oxid

H3C Triphenylphosphine- methylene
Acetone
This reaction is completely regioselective and has the double bond only in one location. This
reaction is also stereo selective because one of the stereoisomer is a predominant product.
For example:-
Page 16 of 35
H H5 C6 C6 H5
H5 C6
H5C6 CH O + (C6H5)3P = CHC6H5 C + C + (C 6H5)3P = O
C6 H5 H
Benzaldehyde phosphonium ylide H H
Trans - form (60%) Cis - form (40%)
Properties of alkenes:
1) Addition of HX to the unsymmetrical alkene: When unsymmetrical alkene is treated

with unsymmetrical reagent (HX) to form two types of alkyl halides.
Anti - Markovnikov rule

R CH2 CH2 X
1 - Haloalkane
R CH CH2 + HX (20%)
Unsymmetrical Markovnikov rule
R CH CH3
alkene
X
2 - haloalkane
(80%)
Markovnikov rule: When unsymmetrical alkene is treated with unsymmetrical reagent then
the positive part of the reagent will be attack on the doubly bonded carbon atom of alkene
which bears more number of hydrogen atoms and negative part will be attack on doubly
bonded carbon atom which bears less number of hydrogen atoms. This rule is called
Markovnikov rule.
R CH CH2 + HX R CH CH3
Unsymmetrical X
alkene 2 - haloalkane
(80%)
Example: R= - CH3, X = -Br
H3C CH CH2 + HBr H3C CH CH3
Propene Br
2 - bromopropane
(80%)
Mechanism: Mechanism if addition of HX to the unsymmetrical alkenes (Markovnikovrule)

takes place in following steps
1) Formation of a carbo-cation. Notice that for alkene, two carbo-cations are possible.
Page 17 of 35
+ -
R CH2 CH2 + :X
0
1 - Carbocation
R CH CH2 + H X (Less stable)
Alkene + -
R CH CH3 + :X
0
2 - Carbocation
(More stable)
2) Attack of halide ion on the more stable secondary carbocation to form 2 - haloalkane
X
+ -
R CH CH3 + :X R CH CH3
0
2 - Carbocation 2 - haloalkane
Where R = alkyl group and X = - Cl, -Br, - I.
The order of stability of carbocations is 30 20 10. Addition of a reagent to an

unsymmetrical alkene proceeds by way of the more stable carbocation.
Anti - Markovnikov rule: When unsymmetrical alkene is treated with unsymmetrical

reagent in presence of peroxide, then the positive part of the reagent will be attack on the
doubly bonded carbon atom of alkene which bears less number of hydrogen atoms and
negative part will be attack on doubly bonded carbon atom which bears more number of
hydrogen atoms. This rule is called Anti -Markovnikov rule. This rule also called Kharash
peroxide effect.
Peroxide (R - O - 0 - R)
R CH CH2 + HX R CH2 CH2 X
Unsymmetrical
1 - haloalkane
alkene
(20%)
Example: R= - CH3, X = -Br
(C 6H5 - O - O - C 6H5)
H3C CH CH2 + HBr H3C CH2 CH2 Br
Propene Dibenzoylpeoxide 1 - bromopropane
Mechanism of Anti Markovnikov rule: Alkenes reacts with HBr in presence of a peroxide
by a free radical mechanism. Following steps are involved.
1) Peroxide dissociates to give alkoxy free radicals
.
R O O R 2R - O
Peroxide radical
Peroxide
Page 18 of 35
2) Peroxide free radical attacks HBr to form a bromine free radical.
. .
R-O + H Br R OH + Br
Bromide free radical

Peroxide free radical
3) Attack of bromine free radical on alkene to give a primary free radical and a secondary
free radical.
Br
.
R CH CH 2
0
. 1 - Free radical (Less stable)
R CH CH2 + Br
Br
.
R CH CH2
0
2 - Free radical (More stable)
The order of stability of free radicals is 30 20 10. Therefore, the more stable 20 free radical
is formed predominantly.
4) More stable 20 free radical attacks the H Br molecule to form anti- Markovnikov product
and a bromine free radical. The bromine free radical goes back to step 3.
Br Br
. .
R CH CH2 + H Br R CH2 CH2 + Br
0 Bromine free radical
2 Free carbon free radical 1 - bromoalkane
Where R = alkyl group
Note:1) Markovnikov addition reaction follows ionization mechanism whereas anti-Markovnikov

addition proceeds by free radical mechanism.
2) The HCl and HI do not give anti Markovnikov products in the presence of peroxides.
This is because
i) The H Cl bond (103 kcal/mole) is stronger than H Br bond (87 kcal/mole). It is not
broken by the alkoxide free radicals obtained from peroxides.
ii) The H I bond (71 kcal/mol) is weaker than H Br (87 kcal/mol). It is broken by the
alkoxy free radicals obtained from peroxides. But the iodine free radicals so formed readily
combine with each other to yield iodine molecules rather than attack the double bond in
alkenes.
Reactions of alkenes:
Page 19 of 35
1) Hydroboration oxidation reaction: Alkenes reacts with borane (BH3) or diborane

(B2H6) in tetrahydrofuran to give trialkylboranes, which is on treatment with alkaline
hydrogen peroxide gives primary alcohol.
THF
3 R CH CH2 + BH3
( R -CH 2 -CH 2)3B
hydroboration
Alkene Borane Trialkylborane
H2O 2 / Base
3R - CH2 - CH 2 - OH + B(OH) 3
Oxidation 0
1 alcohol
Where R = alkyl group
For example, R = - CH3

THF
3 H3C CH CH2 + BH3
hydroboration ( CH 3 -CH 2 -CH 2)3B
Propene Borane Tripropylborane
H2O 2 / Base
3CH3 - CH 2 - CH 2 - OH + B(OH) 3
Oxidation
1 - Propanol
2) Reduction of alkenes: Alkenes undergo catalytic reduction reaction in presence of nickel

or platinum catalyst in hot condition to from alkanes
Catalytic reduction
R CH CH2 R CH2 CH3
Ni / Pt
Alkene Alkane
Where, R = H or alkyl group
For example: 1) R = H
Catalytic reduction
H CH CH2 H CH2 CH3
Ni / Pt
Ethene Ethane
2) R = - CH3
Catalytic reduction
H3C CH CH2 H3C CH2 CH3
Ni / Pt
1 -Propene Propane
3) Oxymercuration Demercuration of alkenes: Mercuric acetate, Hg (O2CCH3)2, and

water add to alkenes in a reaction called oxymeruration. The product of oxymercuration is
Page 20 of 35
usually reduced with sodium borohydride (NaBH4) in a subsequent reaction called

demercuration to yield an alcohol.
Oxymurcuration:
OH
Hg(O - CO -CH 3)2
R CH CH2 R CH CH2
H 2O
Alkene - CH 3COOH OHg C CH3
O
Oxymercuration product
Demercuration:
OH
OH
R CH CH2 Reduction
R CH CH3 + HgOH C CH3
OHg C CH3 NaBH4
Alcohol O
O
Where, R = H or alkyl group.
For, example: R = - CH3
Oxymercuration:
OH
Hg(O - CO -CH 3)2
H3C CH CH2 H3C CH CH2
H2O
- CH 3COOH OHg C CH3
Propene
O
Demercuration:
OH
OH
H3C CH CH2 Reduction
H3C CH CH3 + HgOH C CH3
OHg C CH3 NaBH4
2 - Propanol O
O
4) Epoxidation of alkenes: Alkenes react with oxygen gas in presence silver catalyst at 250 -
4000C to from epoxide.
Page 21 of 35
O
Ag
R CH CH2 + O2 R HC CH2 + AgO

Alkene Epoxide
Where, R = H or alkyl group
For example,
O
Ag
H3C CH CH2 + O2 H3C HC CH2 + AgO

Propene Propylen epoxide
5) Mechanism of oxidation of alkene with potassium permanganate (KMnO4) and

Osmium oxide (OsO4): When alkene is undergo oxidation in presence alkaline solution of
KMnO4 and OsO4 in pyridine to form glycol.
O + O
OH OH
[O] Mn
- O O
MnO4 (aq) R C C R
R R
R R
pH 8 C C R R
R R Glycol
C C
Intermediate complex
R R
Alkene O - O OH OH
[O] Os
R C C R
OsO 4 in pyridine O O
R R R R
C C
Glycol
R R
Where R = H or alkyl group
For examples 1) When R = H
Page 22 of 35
O + O
OH OH
[O] Mn
- O O
MnO4 (aq) H C C H
H H
H H
pH 8 C C R H
H H Ethylene glycol
C C
H H
Ethene O - O OH OH
[O] Os
H C C H
H H H H
C C
Ethylene glycol
H H
2) When R = - CH3
O + O
OH OH
[O] Mn
- O O
MnO4 (aq) H3C C C CH3
H3C CH3
H3C CH3
pH 8 C C CH3 CH3
H3C CH3 2,3 - dimethybutan 2,3 - dio

C C
H3C CH3
2, 3 - dimethyl 2 -butene O O
- OH OH
[O] Os
H3C C C CH3
H3C CH3 CH3 CH3
C C
2,3 - dimethybutan 2,3 - diol
H3C CH3
6) Ozonolysis of alkenes: When ozone is passed through an alkenes in an inert solvent. It

adds across the double bond to form an ozonide. Ozonides are explosive compounds. They
are not isolated. On warming with zinc and water (or dimethyl sulphide), ozonides cleave at
the seat of the double bond. The products are aldehydes, ketones, or an aldehyde and ketones,
depending on the structure of the alkene.
Page 23 of 35
1 2 3
R 3 R R 1 3
R O Zn / H2O R R
O3
4 C O + O C
C C 1 R or (CH 3)2S
R O O 2
4 4
2 R R R
R
Alkene Ozonide
Aldehydes or ketones
Where, R1 =R2 = R3 = R4 = H or alkyl groups
For examples 1) When R1 =R2 = R3 = R4 = H
H H H
H O Zn / H2O H H
O3
C O + O C
C C H or (CH 3)2S
H O O
H H H
H
Ethene Ozonide Formaldehyde Formaldehyde
2) When R1 =R2 = H, R3 = R4 = - CH3
H H CH3
CH3 O Zn / H2O H CH3
O3
C O + O C
C C CH3 or (CH 3)2S
H O O
CH3 H CH3
H
2 -Methylpropene Ozonide Formaldehyde Acetone (ketone)
Mechanism of ozonolysis of alkenes: Its mechanism takes following steps
1) Oxygen gas is exposed to high voltage to form ozone (O3):
V
3O2 2O3
High voltage
Oxygen gas Ozone
2) Ozone reacts with the alkenes to form a molozonide intermediate.
Page 24 of 35
+
O -
O O
O
1
R
R
3 O O
1 3
C C R R
2 4 2 4
R R R R
Alkene Molozonide
3) The molozonide intermediate then breaks down into two fragments.
O
-
+ O
O: O O O
1 3 R
1
C C R
3
R R +
2 4 2
R R
R R
4
Molozonide
Two fragments
4) These two fragments then rearrange to form an ozonide intermediate
-
+ O
O 1 3
O
R O O R
1 3
R C + C R
2 4
R 4 2 O
R R R
Two fragments
Ozonide
5) Reduction of the ozonide with reducing agent (zinc in dimethylsulphide) then results in
cleavage of the ozonide into two carbonyl compounds.
1 3
R O O R R
1
R
3
Zn / H2O or CH3COOH
C O + O C + H2O
4 or (CH 3)2S
2 O 2
R R R R
4
Aldehydes or ketones
Ozonide
( Carbonyl compound)
Importance of ozonolysis of alkenes: Ozonolysis is probably best method for locating the
position of the double bonds in unknown alkenes. The oxygenated carbons in carbonyl
compounds obtained by ozonolysis are the ones that were joined by a double bond in the
original alkenes. Suppose alkenes on ozonolysis gives the carbonyl compounds.
Page 25 of 35
H3C H
C O and O C
* *
H3C CH3
Acetone Acetaldehyde
Joining the oxygenated carbons (marked by asterisk) by a double bond, we get the following
structure of the unknown alkenes.
H3C H
C C
H3C CH3
2 -Methyl - 2 -butene
4) DIENES: Alkenes containing two carbon carbon double bonds are called dienes or
alkadienes.
Examples:
H2C CH CH CH2 H2C C CH CH3
1, 3 - butadiene 1, 2 - butadiene
Classification of dienes: Based on the position of two carbon carbon double bonds, dienes
are classified into following types
1) Isolated diene: If the double bonds are separated by more than one single bond, the diene
is called isolated diene.
For example
H2C CH CH2 CH CH2 H2C CH CH2 CH2 CH CH2
1, 4 - Pentadiene 1, 5 - Hexadiene
2) Conjugated diene: If the double bonds are separated by one single bond, the diene is
called conjugated diene.
For example
H2C CH CH CH2 H3C CH CH CH CH CH3
1, 3 - Butadiene 2, 4 - Hexadiene
3) Cumulated diene: If the double bonds are adjacent to each other, the diene is called
cumulated diene.
For example
Page 26 of 35
H2C C CH CH3 H3C CH C CH CH2 CH3
1, 2 - Butadiene 2, 3 - Hexadiene
Structure of allene (Propadiene): In the structure of allene, the central carbon atom is in sp
hybridization. It is bonded to two other carbon atoms. The terminal carbons are sp2
hybridized.
SP - Hybridized carbon
H2C C CH2
2
SP - Hybridized carbon
1, 2 - Propadiene
(Allene)
The formation of and bonds of allene is shown by orbital structures as below.
SP 2
H -S
2 -S
2
SP - SP 2
SP2 - SP2 SP H

C C
C

H H
Formation of (sigma) bonds
H H

C C C

H
H
Formation of (pi) bonds
The carbon atoms in allene are linear and the bonds formed are perpendicular to
each other. There is no delocalization of electrons. Cumulated dienes are, therefore, less
stable than the conjugated dienes.
Page 27 of 35
H
H
C C
C
H H
H2C C CH2
Structure of allene
Structure of 1, 3 Butadiene:
All four carbon atoms in 1, 3 butadiene are SP2 hybridized. The sp2 hybrid orbitals
overlap with each other and with S orbitals of the hydrogen atoms to form C C and C H
bonds. Since the bonds result from the overlap of trigonal SP2 orbitals, all carbon and
hydrogen atoms lie in one plane. All bond angles are 1200.
DelocalizedMolecular orbita
H
2 2 H H
SP - SP
2 C1 2C
SP
2 2
SP 2 SP - SP
S- - SP 2 C 3 C4
H
H
H
Also, each carbon atom in 1, 3 butadiene possesses an unhybridized P orbital. The

p orbitals are perpendicular to the plane of bonds. The p orbital on C - 2 can overlap with
the P orbitals on C 1 and C - 3. The p orbital can C 3 can overlap with the P orbitals on C
- 2 and C - 4. In other words all four P orbitals overlaps with each other to form a large pi
molecular orbital as shown in fig. each pair of pi electrons is thus attracted, not by two, but
all four carbons.
Small amount of overlap
H H
H H
C1 C2 C4
H C2
C3 C4 C1 C3 H
H
H H Partial double bond
H
The overlap of P orbitals of C 2 and C 3 in both directions, which allows the

electron to be spread over a large area, is referred to as delocalization. This delocalization of
electrons is responsible for greater stability of 1, 3 butadiene.
Page 28 of 35
1, 2 and 1, 4 - addition reactions of 1, 3 - butadiene:
1) Addition of halogen acids: 1, 3 Butadiene reacts with halogen acids (HBr or HCl) to
yield a mixture of two compounds. They are 3 bromo 1 butane and 1- bromo 2 butane.
The first product results from 1, 2 addition to one of the double bonds. The second product
results from addition to terminal (1, 4) positions with the formation of new double bonds
between C -2 and C -3. This latter process is known as 1, 4 addition. At low temperatures
the 1, 2 addition is preferred, whereas at high temperatures 1, 4 addition predominates.
Br
H3C CH CH CH2
3 - Bromo 1 - butene
H2C CH CH CH2 + HBr (1, 2 - addition)
1, 3 - Butadiene H3C CH CH CH2 Br
Bromo 1 - butene
(1, 4 - addition)
2) Addition of halogens: 1, 3 Butadiene reacts with halogens (Cl2 or Br2) in the presence
of an inert solvent (CCl4) to give a mixture of two dibromo compounds.
Br Br
H2C CH CH CH2
3, 4 -Dibromo 1 - butene
H2C CH CH CH2 + Br2 (1, 2 - addition)
1, 3 - Butadiene Br Br
H2C CH CH CH2
1, 4 -Dibromo 2 - butene
(1, 4 - addition)
3) Addition of hydrogen: 1, 3 Butadiene reacts with hydrogen in the presence of a catalyst

to give a mixture of 1- butane and 2 butane.
H2
H2C CH CH CH2 H3C CH2 CH CH2 + H3C CH CH CH3
Pt
1, 3 - Butadiene 1 - Butene 2 - Butene
(1, 2 - addition) (1, 4 - addition)
4) Addition of water: 1, 3 Butadiene reacts with water in the presence of a H2SO4 to give a
mixture of 1- butan-3-ol and 2 butan-1-ol.
Page 29 of 35
+ OH
H
H3C CH CH CH2
1 - buten -3 -ol
H2C CH CH CH2 + H2O (1, 2 - addition)
1, 3 - Butadiene OH
+
H
H3C CH CH CH2
2 - buten -1 -ol
(1, 4 - addition)
5) Polymerization: 1, 3 Butadiene polymerizes in the presence of a peroxide to give

polybutadiene (Buna rubber)
R2O 2
n H2C CH CH CH2 - CH 2 CH CH CH 2 -
n
1, 3 - Butadiene
Polybutadiene
The structure of the polymer suggests that 1, 4 addition predominates
Diels Alder reaction: This involves the treatment of 1,3 butadiene(conjugated diene) with
an alkene or alkyne. No catalyst is required.
The alkene or alkyne used in Diels Alder reaction is referred to as dienophile (Diene
lover). The product of Diels Alder reaction is called the adduct. The net result is the
formation of two new bonds and new bond at the expense of the three original bonds.
For example -
CH2 0
CH2 200 C
+
CH2
CH2
Cyclohexene
1, 3 -Butadiene Ethylene
(Adduct)
(Diene) (Dienophile)
6) Diels Alder reaction of 1, 3 butadiene with maleic anhydride:
O O
CH2 0
100 C
+ O O
CH2
O O
1, 3 -Butadiene Maleic anhydride
(Diene) (Dienophile) (Adduct)
Page 30 of 35
5) ALKYNES: Alkenes are hydrocarbons that contain a carbon carbon triple bond ( C)
in their molecules. They have the general formula CnH2n -2 (n = 2, 3, 4, etc.). These
compounds are highly unsaturated even than alkenes.
Examples:
Value n in CnH2n-2 Structure Name
2 HC CH Acetylene (ethene)
3 H3C C CH Propyne (propyne)
4 H3C CH2 C CH 1 Butyne

H3C C C CH3 2 - Butyne
Methods of preparation of alkynes:
1) By dehydrohalogenation of vicinal dihalides: Compounds that contain halogen atoms on

adjacent carbon atoms are called vicinal dihalides or vic dihalides. Alkynes are obtained by
treatment of vicinal dihalides with alcoholic KOH followed by sodium amide.
H Br H Br
NaNH2
R C C H + KOH R C C H R C C H
(alc.) - NaBr
- KBr Vinyl halide Alkyne
Br H - H 2O - NH 3
Vicinal dihalide
Where R = H or alkyl group.
This method is useful method since the vicinal dihalides are readily prepared from alkenes by
the addition of halogens.
For example: 1) When R = H
H Br H Br
NaNH2
H C C H + KOH H C C H H C C H
(alc.) - NaBr
- KBr 1 - bromo 1 - ethene - NH Acetylene (ethyne)
Br H - H 2O 3
Vicinal dihalide
(1,2 - dibromo ethane)
2) When R = - CH3
Page 31 of 35
H Br H Br
NaNH2
H3C C C H + KOH H3C C C H H3C C C H
(alc.) - NaBr
- KBr Vinyl halide propyne
Br H - H 2O - NH 3
Vicinal dihalide (1 - bromo 1 - propene)
(1,2 - dibromo propane)
2) By dehydrohalogenation of gem dihalides: Compounds that contain two halogen atoms

on same carbon atom are called gem dihalides. Alkynes are obtained by treatment of gem
dihalides with alcoholic KOH solution.
H Br H Br
KOH in alcohol KOH in alcohol
R C C H R C C H R C C H
- KBr
- KBr Vinyl halide Alkyne
H Br - H 2O - H 2O
Gem dihalide
Where R = H or alkyl group.
For example: 1) When R = H
H Br H Br
H C C H H C C H H C C H
- KBr
- KBr 1 - bromo 1 - ethene Acetylene (ethyne)
H Br - H 2O - H 2O
Gem dihalide
(1,1 - dibromo ethane)
2) When R = - CH3
H Br H Br
H3C C C H H3C C C H H3C C C H
- KBr
- KBr 1 - bromo 1 - propene - H 2O Propene
H Br - H 2O
Gem dihalide
(1,1 - dibromopropane)
3) Preparation of higher alkynes from terminal alkynes: This method contains two steps
Step 1) Preparation of sodium salt of terminal alkynes: Sodium salts of terminal alkynes
are prepared by treatment of 1 alkynes with sod amide in liquid ammonia.
Liquid NH3
R C C H + NaNH2 R C C Na + NH3
1 - Alkyne Sodium salt of 1 - alkyne
Page 32 of 35
Step 2) Preparation of higher alkynes: Sodium salt of alkynes is treated with primary alkyl
halide to form higher alkynes.
1 1
R C C Na + R X R C C R + NaX
0
Sodium salt of 1 - alkyne 1 - Alkyl halide Alkynes
Where R = H or alkyl group, R1 = Alkyl group and X = -Br, - Cl
For example: When R = H, R1 = - CH2CH3 and X = -Br
Step 1) Preparation of sodium acetylides:

Liquid NH3
H C C H + NaNH2 R C C Na + NH3
Acetylene Sodamide Sodium acetylides
Step 2) Preparation of higher alkynes:

H C C Na + H3C CH2 Br H C C CH2 CH3 + NaX
Sodium salt of 1 - alkyne Ethyl bromide 1 - Butyne
Reactions of alkynes:
1) Metal ammonia reduction of alkynes: To form a trans- alkenes, when alkynes is undergo
reduction with sodium metal in liquid ammonia. During the reduction, two hydrogens must
be added to the alkynes with anti stereochemistry.
R H
1 Na
R C C R + [H] C C
Liquid NH3 1
Alkyne H R
Trans - Alkene
Where R = R1 = Alkyl group
For example: When R = R1 = - CH3
H3C H
Na
H3C C C CH3 + [H] C C
Liquid NH3
2 - Butyne H CH3
Trans - 2 - butene
Significance of this reaction: This method is used to convert alkynes to trans alkenes
2) Oxidation of alkynes with KMnO4: The oxidation of alkynes with alkaline potassium
permanganate cleaves the molecule at the site of the triple bond to form carboxylic acids.
Acetylene under these condition yields oxalic acid. This degradation reaction of alkynes is
useful in determining the structure of alkynes.
Page 33 of 35
1 KMnO4 1
R C C R + 4[O] R COOH + R COOH
Base
Alkyne Carboxylic acid Carboxylic acid
Where, R = R1 = H = alkyl group
For examples 1) When R = - CH3, R1 = H
KMnO4 COOH
H C C H + 4[O]
Base COOH
Acetylene (Ethyne)
Oxalic acid
2) When R = - CH3, R1 = H
KMnO4
H3C C C H + 4[O] H3C COOH + CO 2
Base
1 - Propene Carboxylic acid
3) When R = - CH3 = R1
KMnO4
H3C C C CH3 + 4[O] H3C COOH + H3C COOH
Base
2 - Butene Acetic acid Acetic acid
Acidic nature of terminal alkynes: Terminal alkynes are weak acidic in nature compare to
strong base. This is due following reason.
1) Terminal hydrogen of 1 alkyne can be readily removed by means of strong base. Hence
1- alkyne is considered as weak acids.
- -
R C CH + NH 2 R C C + NH 3
1 - alkyne Carbonion
(T erminal alkyne)
2) Terminal alkyne is more acidic than the alkene and alkane because value of these
increases in that order.
C C H C C H C C H
Alkanes Alkenes Alkynes
= 62
3) Greater the S character in a hybrid orbital containing a pair of electrons, the basic is that
pair of electrons and the more acidic in nature. S Character is increases in the order of
Page 34 of 35
C C C C C C
2 SP
3 SP
SP
25% 33% 50%
Therefore terminal alkynes are more basic in nature the alkenes which is more than alkanes.
Page 35 of 35
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
Chapter 6: Liquids and Solutions 9 hours
Properties of liquids: Surface tension and its determination using

stalagmometer. Viscosity of a liquid and determination of coefficient of viscosity
using Ostwalds viscometer. Effect of temperature on surface tension and
coefficient of viscosity of a liquid (qualitative treatment only).
Solutions of liquids in liquids: Thermodynamics of ideal solutions and
Raoults law.
Non-ideal solutions: Vapour pressure-composition and temperature
composition curves of ideal and non-ideal solutions. Distillation of solutions-
Lever rule, azeotropes. Partial miscibility of liquids. Critical solution
temperature. Immiscibility of liquids. Principle of steam distillation, Nernst
distribution law and its application. Solvent extraction.
Solutions of gases in liquids: Henrys law of gas solubility and its
applications
Solutions of solids in liquids: Colligative properties - Review of colligative
properties, Raoults law of relative lowering of vapour pressure and its
limitations. Determination of molecular mass of a solute by (i) Berkeley-
Hartleys method (), (ii) Beckmanns method (Tf) and (iii) Landsbergers
method (Tb). Abnormal molecular masses, vant-Hoffs factor i and its
significance.
Introduction: Anything which can occupy the space is called matter. Matter
usually exists in three states namely solid, liquid and gases. In solids, the
molecules are held rigidly with strong interactive force close packed as a result
there is no space between the solid molecules. Hence there is no movement of
molecules but can vibrate about fixed points. Therefore solid possesses a
definite shake and volume and are incompressible on applying pressure.
In gases, the molecules are held with weak interactive force as a result there
is large space between the gases molecules. Hence there is most free movement
of molecules is takes place. Therefore, gases possess no definite volume and no
definite shape and they are most compressible on applying pressure.
In liquid the molecules are held with less strong interactive force compare to
in solid as a result there is small space between the liquid molecules. Hence
there is free movement of molecules takes place. Therefore liquid possess a
1
definite volume but no definite shape and are less compressible on applying
pressure.
In general, liquid is the intermediate phase (state) between solid and liquid.
Physical properties of liquids: The following two important properties of
liquid
1) Surface tension of a liquid and 2) Viscosity of a liquid
1) Surface tension of a liquid: Surface tension is the characteristic property of

every liquid and it is due to intermolecular attractions among molecules of the
liquid. A molecule in the interior of the liquid is attracted by surrounding
molecules in all directions and hence resultant force on that molecule is zero.
The molecule on the surface of the liquid experiences only the resultant
downward attraction normal to the surface and, therefore, surface tends to
acquire minimum surface area. Thus, the surface of liquid is in a state of
tension. The force causing this strain is called surface tension. It is defined as
the force in dynes acting at right angle to the surface of a liquid along 1 cm
length of the surface. Its unit is dynes /cm. its S.I. unit is Nm-1. It is denoted
by Greek letter gamma ( ).
The measurement of surface tension of liquid is based on the fact that the
drop of liquid at the lower end of capillary falls down when weight of the drop
becomes just equal to the surface tension. Thus,
a) The force of gravity to pull the drop downward = v g
Where v and are volume and density of the drop respectively and g is the
acceleration due to gravity.
b) Force tending to uphold the drop = 2 r where 2 r is the circumference of a
circular surface of radius r and is its surface tension.
At equilibrium, when the two forces are balanced:
2 r = v g .(1)
If n is the number of drops in volume V of the liquid, the volume of each drop
will be v =
Then from equation (1) we have 2 r = .(2)
Surface tension, can be obtained from this equation.
Determination of surface tension of a liquid using stalagmometer:
The stalagmometer consists of a bulbed dropping tube with capillary. The lower
end of capillary is well ground, polished and flattened called base in order to
provide larger dropping surface. There are two marks, C and D above and
below the bulb B. The upper end of the stalgmometer is connected with a
rubber tube and a screw pinch cork in order to control the rate of flow of the
liquid so that spherical drop may be formed
2
Clean the stalgmometer first with NaOH then with chromic acid and wash
finally with distilled water. Immerse the lower end in a beaker containing
distilled water and suck up water until it rises above the upper mark C. control
the rate of flow of water with the help of screw pinch cock so that the number
of drops falling per minute becomes about 15 -20. Thus adjustment is essential
otherwise the drop will not be properly formed (does not become spherical).
Start counting the drops when the water meniscus just reaches the upper
mark C and stop when the meniscus just passes the lower mark D. take four
readings and then take their mean value.
Now clean the stalgmometer and dry it. Fill it with liquid given until it rises
above the upper mark C and count the number of drops as before.
If be number of drops and be the density of water and be number
of drops and be the density of liquid , in the same volume and same
capillary tube, then we know that,
For liquid
2 r = . (1)
For water
2 r = . (2)
Divide equation (1) by (2) we get,
=
By knowing number of drops of liquid and water and densities of liquid and
water and surface tension of water, we can calculate the surface tension of the
given liquid.
Effect of temperature on surface tension: According to the kinetic theory,
molecular kinetic energy is proportional to absolute temperature. The rise in
3
temperature of a liquid, therefore, is accompanied by increase in energy of its

molecules. Since intermolecular forces decrease with increase in the energy of
molecules, the intermolecular forces of attraction decrease with rise in
temperature. Hence, surface tension of liquid decreases with rise in
temperature. At critical temperature, since the surface of separation between a
liquid and its vapour disappears, the surface tension falls to zero.
Eotvos suggested the following expression for the variation of surface tension
with temperature:
( ) 2/3 = a- kt .(1) Where, M is molar mass, is density, is surface
tension at temperature t; a and k are constants.
At critical temperature, t = and = 0
Then equation (1) becomes
0=ak or a = k then equation (1) becomes ( ) 2/3 =k(
- t) . (2)
Since surface tension vanishes roughly 60 above the critical temperature rather
than at the critical temperature. Ramsay and Shields proposed the following
equation for the temperature dependence of surface tension.
( ) 2/3 = k ( t 6 )
2) Viscosity of a liquid: Viscosity is the property of liquids and gases. The
resistance offered by one part of the liquid to the flow on the other part is
known as viscosity of liquid. It is due to internal friction of molecules and
mainly depends on the nature and temperature of the liquid. In laminar flow,
each layer moves parallel to its adjacent layer without intermixing. The
unparallel flow of layer is called turbulent flow. In the laminar flow, the
resistance force F is directly proportional to the velocity difference between two
adjacent layers, v and the area of the surface, A of contact of two layers and is
inversely proportional to distance (x) between them.
i. e. F or F = where, is constant and is called coefficient of
viscosity of the liquid. If in the above equation A = 1 sq. cm, v = 1 cm.s-1, x = 1
cm, then, F = . Hence (eta) is defined as the force necessary to maintain a
velocity difference of unity between two adjacent parallel layers of liquid, 1 cm.
apart and having area of surface of constant unity. Its unit is poise and smaller
unit is centipoise. S.I. unit of viscosity is Nsm-2.
The measurement of viscosity by viscometer is based on the Poisuilles
equation, which is
= . (1) Where, v = volume of liquid, t = time for flow

through the capillary tube of radius r and length l, p = hydrolytic pressure
of the liquid = h g . Then equation (1) becomes
= . (2)
Where, g is acceleration of gravity, h is height from ground and is density of
liquid.
4
Determination of viscosity of a liquid using Ostwalds viscometer:

Ostwalds viscometer is U shaped glass tube as shown in the figure. In one
arm, the bulb A is connected with a fine capillary. The lower end of the
capillary is connected with a U tube provided with a larger bulb B in the
second arm. The bulbs are necessary to maintain the hydrostatic pressure
during flow of the liquid. Through the capillary tube, the liquid flows with a
measurable speed. There are two marks C and D above and below the bulb A.
the upper end of the bulb A is attached with a rubber tube. The liquid flows
under its own weight.
Clean the viscometer with chromic acid and then thoroughly with
distilled water. It is finally washed with alcohol or ether and then dried. A
sufficient volume of distilled water is introduced by pipette in bulb B so that
bend portion of tube and half or a little more than half of bulb B are filled up.
Clamp the viscometer in a vertical position. Through the rubber tube attached
to upper arm of a bulb A, suck the water until it rises above the upper mark C
and allow it to flow under its own weight. The time of flow f water from C to D
is measured by starting the stop clock as the meniscus of the liquid just
reaches upper ma C and stopping the clock as the meniscus just passes the
lower mark D. take at least 3 to 4 readings with water and then take their
mean value.
If and be time taken to flow liquid and water and and are
their densities in the same viscometer of radius r volume v and length l.
Then we know that from Poisuilles equation (2). For liquid:
= . (3)
For water:
5
= . (4)
Divide equation (3) by (4) finally we get,
= where, and are the viscosities of liquid and water

respectively.
By knowing the values of , , , and at room temperature, the
viscosity of the liquid ( can be calculate.
Effect of temperature on viscosity of liquid: The viscosity of a liquid
generally decrease with rise in temperature. The decrease is appreciable, being
about 2 per cent per degree rise of temperature in many cases. This can be
explained using hole theory. According to this theory, there are vacancies or
holes in a liquid. The liquid molecules keep on moving continuously into these
vacancies. As a consequence, the vacancies also keep on moving around as
otherwise the liquid will not be able to flow. This process, however, requires
energy. A liquid molecule, therefore, needs some activation energy to move into
a hole. As the activation energy becomes increasingly available at increasing
temperatures, a liquid can flow more easily at higher temperatures. The
coefficient of viscosity, thus, falls appreciably with rise in temperature.
The relationship between coefficient of viscosity of a liquid and temperature
is expressed mathematically as =A where, A and Ea are

constant for given liquid.
Solution: A homogeneous mixture of two or more substances having uniform
properties throughout called solution. Since it is a homogeneous mixture,the
solution constituents a single phase. The substances of which the solution is
made are called its components. Solutions are generally two component (or
binary) systems consisting of a solute and solvent. The solute is the component
present in smaller proportion that dissolves to form the solution. The solvent,
on the other hand, is the component present in larger proportion in which the
solute dissolves.
Types of solutions: Based on the nature of solute and solvent, solutions are
classified into three types namely, 1) Solutions of liquids in liquids, 2)
Solutions of gases in liquids and 3) Solutions of solids in liquids.
I) Solutions of liquids in liquids: The homogeneous mixtures of only two
components which are in liquid states are called binary solutions of liquids in
liquids. Both the liquids are supposed to be volatile. In liquid solutions the
molecules are very close together. The solubility of a liquid in another liquid is
determined by the molecular structure of the solute and the solvent. If solute
molecules, exert large intermolecular forces on one another but are not
attracted to the solvent molecules, they tend to stick together forming strongly
a separate phase from that of the solvent. Similarly, if the solvent molecule
attract one another strongly and show no affinity for the solute molecules, the
solvent molecules form a separate phase. For the solute molecules to form a
6
solution with the solvent molecules, the general rule is that like dissolves like.
Two substances having similar molecular structures and similar intermolecular
forces are generally soluble in each other. In general, polar substances dissolve
in polar substances and non polar substances dissolve in non polar
substances.
Concentration units: The concentrations of solutions are expressed in a
number of ways, all of them involving the quantity of the solute and quantity of
solvent or solution.
1) Molarity: Number of moles of the component present in one litre (dm3) of
the solution is called molarity.
2) Molality: Number of moles of the component present in one kilogram (dm3)
of the solvent is called molality.
3) Normality: Number of gram equivalents of the component present in one
litre (dm3) of the solution is called normality.
4) Mole fraction: In a solution containing moles of component 1, moles of
component2, moles of component 3 and so on, the mole fraction, , of the
component is defined as
= = ( ..)
The sum of the mole fractions of the components of a mixture is unity.
=1
5) Mass percent: The mass percent of a component A in solution is defined as
Mass % A = x 100
6) Mole percent: The mole percent of a component A in solution is defined as
Mole % A = x 100
7) Parts per million: The concentration of a component A in solution in parts
per million (ppm) is defined as
= x
Raoults law of vapour pressure: The partial vapour pressure of any volatile
component of a solution at any temperature is equal to the vapour pressure of
the pure component multiplied by the mole fraction of that component in the
solution. This statement is called Raoults law of vapour pressure.
Suppose a binary solution is made of mole of a volatile liquid A and
moles of a volatile liquid B. If and are partial pressures of the two liquid
components, then according to Raoults law,
= and =
Where, is the mole fraction of the component A given by /( , is
the mole fraction of the component B given by /( and and are
the vapour pressures of pure components A and B respectively.
Classification of solutions of liquids in liquids: Solutions of liquids in liquids

are classified into two types;
1) Ideal solutions: The solutions which obey Raoults law over the entire
range of concentration and temperatures are known as ideal solutions.
7
i. e. p = + = + where P is the total vapour pressure of

solution.
Since + = 1, =1- and =1-
P= (1 - +
P= + and P = +
Characteristics property of ideal solution:

1) The enthalpy of mixing of the pure components to form the solution is zero
i.e. =0
2) The volume of mixing is also zero, i.e. =0

It means that no heat is absorbed or evolved when the components are mixed.
Also, the volume of solution would be equal to the sum of volumes of the two
components. At molecular level, ideal behavior of the solutions can be
explained by considering two components A and B. In pure components, the
intermolecular attractive interactions will be of types A-A and B-B, whereas in
the binary solutions in addition to these two interactions, A-B type of
interactions will also be present. If the intermolecular attractive forces between
the A-A and B-B are nearly equal to those between A-B, this leads to the
formation of ideal solution. A perfectly ideal solution is rare but some solutions
are nearly ideal in behavior.
Examples:1) Solutions of n-hexane and n-heptane 2) Solution of bromoethane
and chloroethane 3) Solution of benzene and toluene.
Vapour pressure composition curve of ideal solution: Vapour pressures of
components (A is more volatile than B) are plotted against mole fraction
(composition) at constant temperature which gives a straight line.
+ pB B1
Vapour pressure
P = pA
Vapour pressure
0
1 pA
A = XA
pA
pA =
XB p 0
B
A=1 Mole fraction (composition) B=1

B=0 A=0
B B1 curve represent the partial vapoure pressure of B component, AA1 curve

represent the partial vapour pressure of A and A1B1 curve represent the total
vapour pressure of the solution.
8
From the vapour pressure composition diagrams, P= +

and P= + gives the relationship between total vapoure
pressure and mole fraction of the components in the solution. It is easy to find
out the relation between the composition of vapour above the solution and the
composition in the solution.
Suppose is the mole fraction of A in vapour phase and is the mole
fraction of B in the solution, then
= = = =
Similarly mole fraction of B in solution is given as
If component A is more volatile than B, then and
In other words the vapour is richer in more volatile component B than in the
solution.
2) Non ideal solutions: The solutions which do not obey Raoults law over the
entire range of concentration and temperatures are known as non- ideal
solutions.
i. e. p +
Since + = 1, =1-
P (1 - + and P (1 - +
+ and +
Characteristics property of non- ideal solution:

1) The enthalpy of mixing of the pure components to form the solution is not
equal to zero i.e. 0
2) The volume of mixing is also not equal to zero, i.e. 0
It means that heat is absorbed or evolved when the components are mixed.
Also, the volume of solution would not be equal to the sum of volumes of the
two components. At molecular level, non ideal behavior of the solutions can be
explained by considering two components A and B. In pure components, the
intermolecular attractive interactions will be of types A-A and B-B, whereas in
the binary solutions in addition to these two interactions, A-B type of
interactions will also be present. If the intermolecular attractive forces between
the A-A and B-B are not equal to those between A-B, this leads to the
formation of non- ideal solution. The perfectly non-ideal solutions are the real
solutions.
Examples: 1) Solutions of cyclohexane and carbon tetrachloride 2) Solution of
ethyl alcohol and chloroform 3) Solution of water and sulphuric acid.
9
Types of non ideal solution: Non- ideal solution may be divided into three
types.
1) Type I non ideal solution: The solution of type I show small positive
deviations from ideal behavior, the vapour pressure of each component being
only slightly greater than that predicted by Raoults law. The total vapour
pressure in such cases remains always within the vapour pressures of the pure
components. This is shown in vapour pressure composition curve of
cyclohexane carbon tetrachloride.
+ pB B1
Vapour pressure
P = pA
Vapour pressure
0
1 pA
A = XA
pA
pA =
XB p 0
B

B=0 A=0
A = Cyclohexane B = Carbon tetrachloride
2) Type II non ideal solution: The solution of type II show large positive
considerably greater than that predicted by Raoults law. The total vapour
pressure curve rises to a maximum which is above the pressure of each of the
pure components. This is shown in vapour pressure composition curve of
acetaldehyde carbon disulphide.
B1
Vapour pressure
Vapour pressure
A1

B=0 A=0
A = acetaldehyde B = Carbon disulphide
Positive deviations occur when the interaction between unlike molecules is

weaker than the interaction between like molecules.
10
3) Type III non ideal solution: The solution of type III show large negative
considerably lesser than that predicted by Raoults law. The total vapour
pressure curve dips to a minimum which is below the pressure of each of the
pure components. This is shown in vapour pressure composition curve of
acetone chloroform.
B1
Vapour pressure
Vapour pressure
A1

B=0 A=0
A = acetone B = Chloroform
Negative deviations occur when the interaction between unlike molecules is

stroger than the interaction between like molecules.
Differences between ideal and non ideal solutions

Ideal solution Non- ideal solution
1) It obeys Raoults law at all 1) It does not obey Raoults law at all
concentrations and at all concentrations and at all
temperatures. temperatures.
2) Enthalpy of solution not change on 2) Enthalpy of solution change on
mixing mixing
i.e. =0 i.e. 0
3) Volume of solution not change on 3) Volume of solution change on
mixing mixing
i.e. =0 i.e. 0
Ex. Solution of benzene and toluene. Ex. Solution of water and sulphuric
acid
11
Vapour pressure composition and temperature composition curves of

completely miscible binary solutions: Consider a binary mixture consisting
of two liquid components A and B which are completely miscible with each
other. On heating under constant pressure, say, under atmospheric pressure,
it will start boiling at a temperature at which its total vapour pressure becomes
equal to the atmospheric pressure. If P represents atmospheric pressure, then
the condition for boiling is that P = where and represent the
partial pressures of the two components A and B. Since solutions of different
compositions have different vapour pressures, it follows that they will boil at
different temperatures. Evidently, a solution of higher vapour pressure will boil
at a lower temperature and solution of higher vapour pressure will boil at a
lower temperature and vice versa. This makes it possible to draw boiling
temperature composition graphs from the corresponding vapour pressure
composition diagram.
Type - I: Here the vapour pressure changes continuously with composition of
the mixture. Since in type I, the vapour pressure of pure A is the lowest and
that of pure B is the highest,it follows that the boiling point of A will be the
highest and that of B the lowest. Further, since the points also lie in between,
as shown in graph. It is also evident that since, at a given temperature, the
vapour phase will be richer in the more volatile component B, the composition
of the vapour phase will be always richer in B than that of the liquid phase.
Therefore, the vapour composition curve will lie above the liquid composition
curve.
At constant temperature At constant pressure
id B1 A1 va
po
i qu
Vapour pressure
ur
Vapour pressure
temperature
temperature
A1 o ur
Boiling
vap Li q
Boiling
ui d B1
A=1 B=1 A=1 B=1

Mole fraction Mole fraction
B=0 A=0 B=0 A=0
Type -II: Here the vapour pressure shows a maximum in its vapour pressure
composition curve. Since in type II, the vapour pressure curve shows a
maximum for a certain composition, say, C as shown in graph, the solution of
that composition will boil at the lowest temperature. This will give rise to a
minimum in the boiling point curve.
12

C
id A1 va
po
Vapour pressure
i qu 1
ur
Vapour pressure
L B
temperature
temperature
our
vap
Boiling
Boiling
1
A Li q B1
ui d
C
A=1 B=1 A=1 B=1
B=0 A=0 B=0 A=0
Type - III: Here the vapour pressure shows a minimum in its vapour pressure
composition curve. Since in type III, the vapour pressure curve shows a
minimum for a certain composition, say, D as shown in graph, the solution of
that composition will boil at the highest temperature. This will give rise to a
maximum in the boiling point curve.
D va p
ou
Vapour pressure
1
r
Vapour pressure
B
1
A
temperature
ui d
temperature
Li q Li q
ui d
Boiling
1
Boiling
A
ur B1
v apo
D
A=1 B=1 A=1 B=1
B=0 A=0 B=0 A=0
Fractional distillation and the Lever rule of binary liquid solutions:

Consider a two component temperature composition diagram of two
components A and B where we have assumed that B is more volatile than A,
i.e. the boiling point of pure B, , is less than that of pure A, . In this
system, the composition of the liquid and vapour phases can be determined
with the help of Lever rule. We proceed as follow: Take any point, say a in the
two phase liquid vapour (L + V) region. Draw a horizontal line called the tie
line passing through a and let it meet the liquid (liquid + vapour)
equilibrium curve at l and vapour (liquid + vapour) equilibrium curve at v.
13
Then the ratio of the number of moles of liquid phase to the number of moles of
vapour phase is given by
Called Lever rule.
V
TA0
v V+L
a* l
TB0 L
A=0 A=1
B=1 B=0
Azeotropic mixture: A mixture of liquid in liquid boils at constant

temperature and distils over completely at the same temperature without
change in composition is called constant boiling mixture or azeotropic mixture.
For example, mixture of water and ethanol, mixture of water and n-propanol.
Consider the distillation of a mixture of composition represented by x. The first
fraction collected will have the composition shown by x1. Evidently, it will be
richer in the constant boiling mixture. The composition of the residual liquid,
therefore, will shift towards A. As the distillation proceeds, the composition of
the distillate changes towards C and that of the residual solution towards A.
Ultimately by repeated distillation, the mixture of the minimum boiling point of
composition C will be obtained as distillate and the liquid A will be left as
residue in the distillation flask. It will never be possible to have pure B.
14
At constant pressure
A1 va
po
ur
temperature
temperature
Boiling
Boiling
Li q B1
ui d
x x1
C y1 y
A=1 B=1
Mole fraction
B=0 A=0
If on the other hand, a mixture of composition indicated by Y is distilled, the

composition of the first fraction will be as represented by y1. Evidently, it will be
richer in the constant boiling mixture. Therefore, the composition of the
residual liquid will become richer in B. As the distillation proceeds, the
successive fractional distillates will become increasingly rich in the constant
boiling mixture while the residual liquid will become increasingly rich in the
pure component B. Ultimately, by repeated fraction distillation, the constant
boiling mixture will be obtained as the distillate and the pure liquid B as the
residue in the distillation flask. It will never be possible to have pure A in this
case.
Partial miscibility of liquids: The temperature above (or below) which a pair
of partially miscible liquids becomes miscible in all proportions is called critical
solution temperature (CST) or consolute temperature for the pair. Some liquid
pairs attain complete miscibility above a certain temperature in which case
they are said to have the upper critical solution temperature (UCST). While
some liquid pairs show complete miscibility below a certain temperature when
they are said to have lower critical temperature(LCST). On the other hand,
some liquid pairs show both UCST and LCST. All partially miscible liquid pairs
have, in general, an upper or a lower CST. However, the upper CST cannot be
realized if one or both the components boil out before it is reached and the
lower CST may not be observed if one or both the components freeze out before
it is reached. Thus, under atmospheric conditions none of the CSTs is observed
for ether water system.
Therefore there are four types of partial miscible liquid liquid systems have
been observed. These are,
1) Those in which the partial miscibility increases on increasing the
temperature. Examples including phenol water, aniline water, aniline
hexane, methanol carbon disulphide and cyclohexane methanol systems. At
and above a certain temperature, the liquids become completely miscible.
Consider a partially miscibility temperature of phenol water system.
15
UCST
Temperature in 0C
68.1
0 36.1 100
of phenol
Phenol - water system
2) Those in which the partial miscibility increases on lowering the temperature.

Examples including diethyl amine water and triethyl amine -water systems.
At and below a certain temperature, the liquids become completely miscible.
Consider a partial miscibility temperature of triethylamine water.
Temperature in 0C
Two phases
18.5
LCST One phase
0 100
of Triethylamine
Triethylamine - water system
3) Those in which the partial miscibility increases on both rising as well as

lowering the temperature. Examples including nicotine water and -picoline
water systems. These liquid pairs show completely miscibility both above and
below certain temperature.
Consider a partial miscibility temperature of nicotine water.
16
UCST One phase

208
Temperature in 0C
Two phases
60
LCST One phase
0 100
of Nicotine
Nicotine - water system
4) Those in which complete miscibility temperature cannot be obtained. A

common example is ether water system.
Distillation of Immiscible liquid systems: In a mixture of two immiscible
liquids each liquid behaves independently of the other. Hence the properties of
each liquid will be unaffected by the presence of other. Consequently the
vapour pressure of mixture of two immiscible liquids would be the sum of
vapour pressures of individual pure components at that temperature.
are partial pressures of pure components then total pressure p is
given by P . The mixture of immiscible liquids boils at lower
temperature than pure liquids.
Since total vapour pressure is constant and independent of composition, the
boiling point of mixture remains constant as long as they are present together.
As soon as more volatile component is boiled away the boiling point will rise to
that of less volatile component.
Let XA and XB be the mole fractions of the two components A and B in vapour
phase and be their partial pressures at the boiling temperature T.
Then according to Daltons law of partial pressure.
P = P (P =Total pressure)
..(1) Where, are the weights of A and B
are the molecular masses of A and B.

Thus the masses of two distillates depend upon the molar masses and the
vapour pressures of pure components. This equation is used for steam
distillation of liquids.
17
Steam distillation: The process of steam distillation is quiet useful and is

generally employed to immiscible liquids which have either higher boiling
points or decompose before their normal boiling point is reached. The liquid to
be steam distilled should have fairly high volatility near the boiling point of
water. Steam is generally passed through the liquid to be steam distilled. When
the temperature is raised high enough to make the
mixture distills with a composition given by the equation
Where, are the weights of A and B, are the molecular

masses of A and B
Nernsts distribution law: When a solute distributes itself between two

immiscible solvents in contact with each other, there exists, for similar
molecular species, at a given temperature, a constant ratio of distribution
between the two solvents irrespective of the total amount of the solute and
irrespective of any other molecular species which may be present. This
statement is called Nernsts law.
i. e. Where,
Condition for distribution law:

This law valid under following conditions:
1) This law valid at constant temperature: As the temperature increases,
solubility of solute in the two solvents increases. Hence concentration of solute
in the two solvent increases as a result distribution law not valid. So, to avoid
this mixture should be kept in constant temperature.
18
2) This law valid in dilute solutions: At higher concentration of solute in the

solution, deviate the distribution law.
3) This law valid when two solvents should not miscible.
4) Solute molecule should not undergo dissociation or association with any
solvent.
Deviation of Nernsts distribution law due to following:
1) Association of the solute in one of the solvents:
Solvent -I
X
Conc. C1
Solvent-II
nX (X)n Total conc.C2
Let X represents the molecular formula of the solute. Let it remain as such in
the solvent- I in which its concentration is C1. Suppose it is largely associated
to give the molecules (X)n in the solvent II in which its concentration is C2.
i.e.
Applying law of mass action for equilibrium
, [X] = = constant x
If the solute exists largely as associated molecule which is generally true at

large dilutions, the concentration of the associated molecules, may be
taken as equal to , the total concentration
i.e. and [X] = constant x
Since the distribution law is valid only for concentration of molecular species in
the two solvents, hence,
This equation is used to study the distribution of benzoic acid between water
and benzene. The acid exists almost entirely as (C6H5COOH)2 in benzene but in
normal in water.
2) Dissociation of the solute in one of the solvents:
19
Solvent -I
X
Conc. C1
X A + B Solvent -II
C2 (1- C2C2
Total conc. C2
Let X represents the molecular formula of the solute. Suppose ,it does not
dissociate in the solvent I but dissociates into A and B in the solvent II. Let C1
be its concentration in the first solvent and C2 the total concentration in the
solvent-II. The distribution law is valid only for the ratio of concentrations of
similar molecular species in the two solvents.
Suppose is the degree of dissociation of the solute X in solvent II. Then,
concentration of the various species would be as shown below:
X A + B
C2 (1- C2 C2
Therefore, according to the distribution law
Applications of the Nernst distribution law:

1) It is used to study the association of a solute by using the equation

2) It is used to study the dissociation of a solute by using the equation
3) It is used in the study of distribution indicators.

4) It is used in the study of complex ions.
5) It is used in the study of solvent extraction.
Solvent extraction: The most important application of the distribution law is
in the process of extraction, in the laboratory as well as in industry. In the
laboratory, for instance, it is frequently used for the removal of a dissolved
organic substance from aqueous solution with solvents such as benzene, ether,
chloroform, carbon disulphide, etc. The advantage is taken of the fact that the
20
partition coefficient of most of the organic compounds is very largely in favour

of organic solvents.
We can derive a general formula which enables the calculation of the amount
of the solute that is left unextracted after a given number of operations. Let V
cm3 of a solution containing W gram of solute be repeatedly extracted with v
cm3 of another solvent which is immiscible with the first. Let w1 be the mass of
the solute that remains unextracted at the end of the first operation. Then, KD
will be given by

Similarly, at the end of the second extraction, the amount w2 that remain
unextracted is given by
= [ ]2
In general, the amount that remains unextracted at the end of n operations, wn

will be given by
[ ]n
It is evident that in order to make as small as possible, for a given value of
, n should be as large as possible. But n x v is equal to the total volume of
the extracting liquid available, i.e. it is constant. Therefore, it is better to keep
n large and v small, rather than the reverse. In other words, the efficiency of
extraction increases by increasing the number of extractions using only a small
amount of the extracting solvent each time.
21
II) Solutions of gases in liquids: Most of the gases are soluble in water as well
as in some other liquids to a more or less extent. The solubility is generally
expressed in terms of absorption coefficient (a), introduced by Bunsen. This is
defined as the volume of gas reduced to N.T.P. dissolved by unit volume of
solvent at the temperature of the experiment and under a pressure of 1
atmosphere of the gas.
The absorption coefficients of a few gases at 200C in three solvents are given by
Solvent Hydrogen Nitrogen Oxygen Carbon dioxide
Water 0.017 0.015 0.028 0.88
Ethanol 0.080 0130 0.130 3.00
benzene 0.06 0.104 0.165 ..
Factors influencing the solubility of a gas: The solubility of a gas in a
liquid depends upon
1) The nature of the gas and the nature of the solvent: The solubility of a
gas in a given solvent varies considerably with the nature of the gas. Generally
speaking, the gases which are easily liquefied are more soluble in common
solvents. Thus CO2 is more soluble than H2 or O2 in water or in any other
solvent. The gases which are capable of forming ions in aqueous solution are
much more soluble in water than in other solvents. This is illustrated by the
fact that gases like HCl and NH3 are highly soluble in water but in benzene in
which they are not capable of forming ions.
2) The temperature of the gas liquid system: It has been found that under
a constant pressure, the solubility of a gas diminishes with rise in temperature.
3) The pressure of the gas: Although solubility of solids are almost
independent of pressure, those of gases in liquids vary considerably with
pressure. William Henry found that the solubility of a gas at a given
temperature increases directly as the pressure. This conclusion formed the
bases what is known as Henrys law, which may stated as below-
The mass of a gas dissolved per unit volume of a solvent is proportional to
the pressure of the gas in equilibrium with the solution at constant
temperature. This statement is called Henrys law.
If m is the mass of a gas per unit volume of a solvent and p is the pressure of
the gas is equilibrium with the solution, then at constant temperature, then
m P or m = k P Where k is the proportionality constant, called Henrys
constant.
If Henrys law is valid, then the graph obtained by plotting solubility of gas
against the equilibrium pressure of the gas at a constant temperature should
be straight line.
22
Solubility of gas in solvent

*
*
*
*
*
*
Equilibrium pressure
Conditions (limitation) of Henrys law:

1) Pressure is not too be high
2) Temperature is not too be low
3) The gas should not highly soluble and does not dissociate or enter into
chemical composition with the solvent.
Henrys law may also stated that the volume of the gas that dissolved in a
fixed volume of a liquid at constant temperature is a constant and is
independent of the pressure of the gas
From the ideal gas equation
PV = n R T can be written as
PV = RT (m is mass and M is molecular mass of a gas)
V=
is constant from Henrys law, is a constant for gas at constant
temperature so that V is also constant.
Applications of Henrys law:
1) This law is used in the sealing the soda or beverage bottle: Effervescence is
observed when a bottle of soda or beer is opened. This is because before
sealing, the beverage is pressurized with a mixture of air and carbon dioxide.
2) This law is used to study the solubility of gases under different pressures in
blood or lipid fat is of considerable physiological importance for deep water
divers and mountaineers.
3) This law is used when a mixture of gases is brought in contact with solvent
each gas dissolves in proportion to its own partial pressure independent of the
other gases.
23
III) Solutions of solids in liquids: Those solutions are formed by dissolving

solids in liquids called solutions of solids in liquids.
Colligative properties: Colligative properties are those which depend entirely
upon the number of particles of the solute dissolved in a known volume of a
given solvent and not at all upon the nature of the solute.
Examples, 1) Lowering of vapour pressure 2) Osmotic pressure 3) Elevation in
boiling point 4) Depression in freezing point.
Colligative properties applicable only for dilute solutions ).
Lowering of vapour pressure of pure solvent: The vapour pressure of pure
solvent is decreased by adding a non-volatile solute. This can be easily
understood since vapour pressure of a liquid is due to the evaporation of
molecules from the liquid surface. In the case of solution the attraction of the
solvent molecules for the solute molecules being large, they find it harder to
escape from a solution than from pure solvent. Thus the vapour pressure of a
solution is always less than that of the pure solvent at given temperature.
Relative lowering of vapour pressure and Raoults law:
If is the vapour pressure of the solution and that of the pure solvent then
the lowering of vapour pressure is
At given temperature, the ratio of lowering of vapour pressure to the vapour
pressure of pure solvent is called relative lowering of vapour pressure.
i.e. Relative lowering of vapour pressure = = constant. At given
temperature.
Raoults law: The relative lowering of vapour pressure of a solution is equal to
the mole fraction of the solute present in the dilute solution. This statement is
called Raoults law for relative lowering of vapour pressure.
Mathematically,
Where, and are the number of moles of the solute and solvent
respectively. is the mole fraction of the solute.
i.e.
The vapour pressure lowering depends on the number of the moles of the
solute and not upon the nature of the solute. Thus vapour pressure lowering is
a colligative property.
Determination of molar mass of solute from lowering of vapour pressure:
24
If w gram of solute of molecular mass m is dissolved in W gram of solvent

then,
And
Where, M is the molecular mass of solvent.
For dilute solution, and may be neglected in comparison with so

that
and
Molar mass of solute,
Limitation of Raoults law:

This law applicable only for dilute solution.
Determination of molar mass of solute by Hearty - Berkeley method:
The apparatus consist of two concentric tubes; the inner one contains a semi-
permeable membrane of copper ferrocyanide and contains the pure solvent.
The outer tube made of gun metal is provided with a piston to which a pressure
gauge is attached. The inner tube is connected to a capillary tube at one end
and a reservoir of pure solvent at the other end as shown in figure.
25
The solution whose osmotic pressure is to be determined is placed inside the

outer tube. The level of the solvent in the capillary tube falls down when
osmosis starts. A pressure is applied slowly and the solvent level in the
capillary tube is observed. The pressure at which the movement of the solvent
level in the capillary tube is just reversed is noted down from the range which
is taken as the osmotic pressure. This gives the osmotic pressure ( ).
We know that, osmotic pressure,
If w is the mass of the solute dissolved in V dm3 of the solution and has
molecular mass m, then and

And
By knowing the osmotic pressure ( ) of the solution at temperature T, the

molar mass of the non- volatile solute can be calculated.
Determination of molar mass of solute using depression in freezing point
by Beckmanns method:
A simple Beckmann apparatus is as shown in figure. It consists of an inner
freezing tube provided with a side tube for introducing the solute. It is fitted
with Beckmann thermometer and a platinum stirrer. The inner tube is
surrounded by an air jacket to ensure a slower and more uniform rate of
cooling. The entire assembly is then placed inside a wide vessel containing
freezing mixture at a temperature several degrees below the expected freezing
point of the solution and provided with a stirrer.
26
A known mass of the pure solvent is placed in the inner tube. It is cooled
with gentle continuous stirring. As a result of super cooling the temperature of
the solvent will fall by 0.5K below the freezing point. The solvent is stirred
vigorously when the solid separates. The temperature rises rapidly to the
freezing point and remains constant for some time. The highest constant
temperature reached is noted down. The inner tube is then removed, warmed
to melt the solid and a weighed amount of the solute is then introduced the
side tube. The freezing point of the solution is then determined as before. The
difference between the two readings gives the depression of the freezing point
.
The molecular weight (molar mass) of the solute is then calculated using the
expression.
Where, = Mass of solvent = Mass of solute = Molar mass of solute

= cryoscopic constant of water, = Depression in freezing point.
Determination of molar mass of solute using elevation in boiling point by
Landsbergers (Walker-Lumsden) method: In this method, the solution is
heated by passing vapours of pure solvent. This is done to avoid superheating.
The apparatus used is shown in figure. It consists of boiling flask (B)
containing pure solvent. It is connected to graduated tube trough delivery tub.
A thermometer is inserted to graduated tube and it is kept in outer jacket (J). A
hole is made in the bulb of the graduated tube for the overflow of excess of
solution.
To start with a known volume of pure solvent is taken in graduated tube and
vapours of solvent are passed into it form boiling tube. Solvent boils at its
boiling point. Then a known mass of solute is added to graduated tube and
dissolved in small quantity of solvent and again solvent vapours are passed
through the solution. The temperature at which solution boils is recorded
which is boiling point of solution (T20C). Afterwards the tube is cooled and
27
volume of solution is recorded. Knowing the density of solvent, mass of solution

can be calculated (mass = volume X density).
The difference in boiling point of solution and solvent gives elevation in
boiling point. By knowing the mass of solute, molar mass of solute can be
calculated by the formula.
Where, = Mass of solvent = Mass of solute = Molar mass of solute

= Ebullioscopic constant of water, = Elevation in boiling point.
Abnormal molecular weights: Since collegative properties depend upon the
number of particles of the solute, in some cases where the solute associates or
dissociates in solution, abnormal results are obtained.
i) Association: There are many organic solutes which in non aqueous solutions
undergo association, i.e. two or more molecules of the solute associate to form
a bigger molecule. Thus, the number of effective molecules or particles
decreases and consequently the osmotic pressure, the elevation of boiling point
or depression of freezing point is less than that calculated on the basic of single
molecule. For examples, acetic acid in benzene and chloroacetic acid in
naphthalene. The molar masses of solutes in such cases will be higher than the
true molar masses as indicted by their formulae. Thus, the molar mass of
acetic acid in benzene as determined from freezing point depression is 118
instead of 60. It appears therefore, that the molecules of acetic acid exist
largely as (CH3COOH) 2 when dissolved in benzene.
ii)Dissociation: Inorganic acids, bases and salts in aqueous solutions undergo
dissociation i.e. the molecules break down into positively and negatively
charged ions. For instance, NaCl in aqueous solution exists almost entirely as
Na+ and Cl- ions. In such cases, the number of effective particles increases and
therefore, osmotic pressure, elevation of boiling point and depression of
freezing point are much higher than those calculated on the basis of un-
dissociated single molecules
Vant Hoff factor: Vant Hoff in order to account for all abnormal cases
introduced a factor i known as the Vant Hoff factor.
Where collegative property implies osmotic pressure, vapour pressure lowering,

boiling point elevation and freezing point depression.
Since these properties vary inversely as the molar masses of the solute. It
follows that,
28
Degree of association: The fraction of the total number of molecules which

combine to form bigger molecules called degree of association.
Derivation of an expression for degree of association: Consider one mole of
a solute dissolved in a given volume of a solvent. Suppose n simple molecules
combine to form an associated molecule.
i.e.
nA (A)n
Let be the degree of association;

Then, the number of un-dissociated moles = 1-
The number of associated moles =
Total number of effective moles = 1- +

Since collegative property is directly proportional to the number of moles, the
Vant Hoff factor I is given by

or

=
Thus, knowing, value of n i.e. the number of simple molecules which combine
to give one associated molecule and the observed molar mass, the degree of
association as well as, can be easily calculated.
Significance of Vant Hoff factor: It gives the idea about whether the
molecules are undergoing dissociation or association.
Degree of dissociation: The fraction of the total number of molecules which
dissociate, i.e. break into simpler molecules or ions called degree of
dissociation.
Derivation of an expression for degree of dissociation: Consider an
electrolyte dissociating to gives rise to n number of ions. If be the
29
degree of dissociation then the equilibrium existing in solution can be

represented as
Ax By xAy+ + yBx-
1- nn
Where, n = total number of ions produced by dissociation of molecule of an

electrolyte. No. of particles which are in dissociated state = n
No. of particles not dissociated = 1-
Total No. of particles present = 1- + n
= 1+ (n- 1)
From Vant Hoff factor

This equation is used to calculate the degree of dissociation of an electrolyte.
Problems:
30
Liquids and Solutions 9 hours

Properties of liquids-Viscosity, Surface tension and Parachor-Definition, mathematical
expression, numerical problems and factors affecting them.
Viscosity- Definition, mathematical expression, Coefficient of viscosity, effect of temperature,
size, weight, shape of molecules and intermolecular forces on it.
Surface Tension-Definition, mathematical expression, effect of temperature and solute on it
Parachor-Definition, Sugen equation, calculation and applications. Numerical problems.
Liquid Mixture: Review of Raoults law, ideal and non-ideal solutions.
Completely miscible liquids-Fractional distillation Tc curves for all the three types, azeotropic
mixtures -examples.
Completely miscible liquids-Critical solution temperature (Three types), examples. Effect of
addition of salt on CST of phenol-water system.
Immiscible liquids-Steam distillation and its applications.
Distribution law-Statement, partition coefficient and condition for validity of distribution of
distribution law. Application-solvent extraction
Dilute solutions- Review of colligative properties and concentration terms
Determination of molecular mass of a solute by: (i) Berkeley-Hartleys method (); (ii)
Beckmanns method (Tf) and (iii) Landsbergers method. Numerical problems.
31
IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
Chapter 7: Environmental Chemistry 4 hours Maximum Marks: 6 - 8
Depletion of ozone in the stratosphere. Causes and remedial measures. The

green house effect and its consequences. Acid rain; photochemical smog.
Treatment of sewage and industrial effluents. Disposal of radioactive wastes.
Introduction: Environmental chemistry is defined as a branch of chemistry

that deals with the study of sources, reactions and effects of chemical species
on air, water and soil. It is a multidisciplinary science involving chemistry,
physics, life sciences, medicine, agriculture and public health.
Components of environment: The accessible components of the environments
are
1) Atmosphere: The atmosphere refers to gaseous layers around earth which
support life on the earth and save us from the environments of outer space.
The atmosphere absorbs most of the harmful radiations from the outer space
and keeps heat balance of the earth to sustain life on the earth.
2) Hydrosphere: The hydrosphere refers to all kind of sources of water, such
as oceans, rivers, lakes, glaciers, polar ice caps, ground water, etc. most of the
earths water (96%) is contained in oceans and this water is unfit for human
consumptions due to high salt content.
3) Lithosphere: The lithosphere refers to earths crusts containing the outer
mineral cover up to a depth of about 16 km. It comprises soil, minerals, air,
water and some organic matter.
4) Biosphere: The biosphere refers to the domain of living organisms in contact
with the atmosphere, hydrosphere and lithosphere. Activities of living
organisms influence environments and vice versa.
For example, oxygen and carbon dioxide content depends a great deal on
animal and plant kingdom through photo-synthesis, decay and respiration.
Components of atmosphere: Atmosphere can be divided into the following
components-
1) Troposphere: The position of the atmosphere closet to the earth is called
troposphere. The troposphere extends upwards to a distance of about 11
kilometers. The troposphere contains about 70% of the mass of the
atmosphere. The important chemical constituents of the troposphere are N2,
O2, CO2, noble gases and water vapours. Its density decreases as one rises
above the earth.
Page 1 of 11
2) Stratosphere: The region beyond 11km up to an altitude of about 40 km is

known as stratosphere. Here the temperature increases with increase in
altitude. Ozone is the important chemical compounds of this region which
absorbs ultraviolet radiation and raises the temperature in the zone. This act of
ozone protects us from the harmful effects of suns ultra-violet radiation.
3) Ionosphere: The region beyond stratosphere is dominated by + ve ions such
as O2+, O+ and NO2+ and free electrons. It is known as ionosphere. Ions can
persist independently so long as ultraviolet radiations from the sun are
available. In the absence of ultra violet radiations at night, +ve ions recombine
with electrons to form neutral species in regions of higher concentration of
ions.
4) Mesosphere: Mesosphere extends from about 40 km to an altitude of about
80 km. Here, once again, the temperature decreases with increase of altitude
due to low level of ozone.
5) Thermosphere: It extends from about 80km. Here, atmospheric gases split
into atoms and undergo ionization after absorption of solar radiations. Here
temperature increases with increase in altitude and show a maximum of
12000C.
All above segments can be shown in the following diagram
Height above earth's surface(km)
110 Thermosphere
100 0.001
90
Ionosphere = Mesosphere 0.01
80
pressure(milibars)
+ Thermosphere 0.1
70
60 Mesosphere
1
50
40 Stratosphere 10
30 seat of O3
20 100
10 Troposphere
1000
-100 -75 -50 -25 0 25 50
0
Atmospheric temp. ( C)
Depletion of ozone layer: A layer of ozone is present at an altitude of 25 30

km from earths surface in the stratosphere. Ozone layer absorbs ultraviolet
radiations from the sun. The presence of ozone in the atmosphere serves as a
Page 2 of 11
shield to protect living organisms on earth from the harmful effects of the ultra
violet radiations. The ultra-violet radiations are known to cause skin cancer
particularly in white males. A decrease in the concentration of ozone would
increase the flux of the radiations which in turn, would increase the rate of
skin cancer.
Ozone is formed by photo dissociation of oxygen molecules by solar
radiation.
h
O2 O+O
UV radiations
O2 + O + M O3 + M
Where M is inert body like N2, O2, etc. which takes away the excess energy
liberated in the reaction thus stabilizing the O3 molecule formed.
The depletion of ozone layer is believed to be caused mainly by-
1) Effects of oxides of nitrogen on ozone layer: The oxides of nitrogen
catalyze the decomposition of ozone and are themselves regenerated to repeat
the cycle.
NO + O3 NO 2 + O2
NO 2 + O NO + O2
O3 + O O2 + O2
The above reactions destroy about 70% of ozone formed in the atmosphere. A
larger concentration of NO in the atmosphere leads to a greater depletion of
ozone. Both flights of supersonic aircrafts and tests of nuclear weapons
generate high temperatures in the atmosphere. At these high temperatures,
nitrogen in the atmosphere is oxidized to oxides of nitrogen.
NO + O2 2NO
2NO + O2 2NO2
The concentration of NO in the stratosphere is thus increased which is turn
result in a larger depletion of ozone layer.
2) Effect of chlorofluorocarbons on ozone layer: Chlorofluorocarbons like
CFCl3, CF2Cl2 and CF3Cl are commonly known as freons. These are used as
refrigerants, aerosol propellants, solvents for cleaning electronic components,
fire fighting agents and packing materials due to these having inert, non toxic,
noncombustible, volatile and easy liquefied characters.
Formation of Freons:
SbFI4 CCl 3F + HCl
CCl 4 + HF
SbFI4
CCl 3F + HF CCl 2F2 + HCl
Although Freons are very stable and long lived in environment, these undergo
photolysis in the upper atmosphere as follows
Page 3 of 11
h .CFCl + Cl.
CFCl 3 (190 -200 nm) 2
h .
CF 2Cl 2 CF 2Cl + Cl.
(g) (g)
Like NO, Cl. formed above reacts with ozone to form oxygen.
Cl . + O3 ClO. + O2
ClO. + O Cl . + O2
O3 + O O2 + O2
Along with the liberation of above oxygen, there is regeneration of atomic
chlorine which acts as catalyst. Present evidence shows that ClOx cycle may be
three times more efficient than NOx cycle in the destruction of ozone.
NOx ClOx
O3 + O O2 + O2 O3 + O O2 + O2
Thus, space from which the ozone layer gets depleted is known as ozone
hole. Many O3 molecules can be destroyed for each Cl atom produced. It has
been shown that for each Cl atom produced; over one thousand ozone
molecules can be destroyed. It was found in the early eighties that a large
ozone hole has been created in the ozone layer over Antarctica.
Causes of ozone depletion:
The concentration of O3 in the stratosphere is only about 10 ppm but is enough
to absorb UV radiations. Ozone absorbs UV radiations of wavelength 200-300
nm and dissociates back to oxygen molecules. Ozone thus allows only small
fractions of suns ultraviolet radiation to reach the earths surface thereby
protecting living beings from radiation damage.
The ultra violet radiations causes following:
1) It causes skin cancer and eye diseases in human beings
2) It cause genetic mutation in plants, animals and marine life
3) Destroy crops and other forms of vegetation.
Remedial measures of ozone depletion:
Methods involved to Control the release of chlorofluorocarbons.
1) Release of chlorofluorocarbons and other ozone depletion substances in the
atmosphere should be banned.
2) Chlorofluorocarbons should be replaced by hydro fluorocarbon which does
not contain chlorine atom.
3) Conversion of Chlorine monoxide radical to chlorine radical cycle present in
the atmosphere can be stopped by combining nitrogen dioxide with carbon
monoxide radical and chlorine radical with methane.
ClO . + NO2 ClONO2 (chlorine nitrate)
Cl. + CH4 .
CH3 + HCl
This stops the chain reaction.
Methods involved to Control the release of NOx.
1) Power plants and industrial processes emit large amount of NOx. Such an
emission can be reduced by
Page 4 of 11
a) Fuel is fired at relatively higher temperatures using less than stoichiometric

amounts of air to reduce the yield of NO
b) Fuel burn out is completed at relatively lower temperature in excess air to
hinder formation of NO
2) NOx in vehicle exhaust is converted into N2 and trace of amount of NH3 with
the help of platinum catalyst.
3) Acidic scrubbing process for the removal of NO2 can also be worked out as
under.
a) Fuel gas containing NO, NO2 and SO2 is introduced with an oxidizer.
NO 2 + SO2 + H2O H2SO4 + NO
b) NO and NO2 react to form N2O3 which is scrubbed by H2SO4 as follows

NO 2 + NO N2O3
N2O3 + 2H2SO4 2NOHSO4 + H2O

The cleaned fuel gas is released into air.
c) NOHSO4 is then decomposed in separate chamber and the resulting H2SO4 is
reused
2NOHSO4 + 1/2 O2 + H2O 2H2SO4 + 2NO2
d) NO2 is then converted into HNO3
3NO2 + H2O 2HNO3 + NO
and excess NO and NO2 are recycled into the oxidizer in step(a)
4) NOx in fuel gases can be removed by alkaline scrubbing solutions containing
Ca(OH)2 and Mg(OH)2.
Green house effect: Carbon dioxide is produced by burning of fossil fuels,

from exhaling of human beings and animals and by the action of acids on
metal carbonates and bicarbonates. Normally carbon dioxide is harmless and
is not a pollutant. However, excess of it can lead to increase in temperature of
the earths atmosphere. This effect known as green house effect.
The earth receives a large amount of energy from the sun. Out of the
total energy received about 66% is absorbed by the earth while the rest 34% is
reflected back into the space. Spectroscopic evidences shows that the earth
absorbs only visible radiations and reflect back infra red radiations. Infra red
radiations are heat radiations. CO2 gas allows short wave radiations like visible
and UV radiations of sun to pass through it but impedes (hinders) the passage
of long wave radiations. Thus, atmospheric CO2 acts as a barrier against the
flow of heat from the earth to the atmosphere. The reflected heat radiations
would thus increase the temperature of the earths surface. It is called green
house effect because like CO2, the glass of a green house allows short wave
radiations from the sun to pass through it but impedes the passage of long
wave radiations I.R. or heat radiations. As a result the temperature of the
rooms of green house increases. If the concentration of CO2 becomes double in
the atmosphere, the temperature of the atmosphere increases by 1.9 0C. It may
Page 5 of 11
be noted that some of the above I.R. radiations reflected by earth are absorbed
by CO2 gas in the atmosphere and does not allow it to dissipate in atmosphere.
We know that the temperature of the earth is balanced equilibrium between the
energy received from the sun and the energy radiated back into space. Thus,
absorption of energy by CO2 could affect the earths climate, resulting in the
melting of polar ice caps, alter the patterns of cropping, changing of biological
activity of oceans, flooding of coastal planes, etc.
Gases other than CO2 which can cause green house effect are CH4, N2O and
chlorofluorocarbons (CFC).
Consequences (effects) of green house effects:
1) Green house effects are responsible for keeping our planet warm.
2) The rise I temperature may lead to climate changes. For example, there may
be less rainfall in temperate zones and more rainfall in the drier areas of the
word. It may also lead to rise in sea level due to increased rate of melting of
glaciers. It has been estimated that the sea level may rise by 0.5 m to 1.5 m in
the next 50 to 100 years. Higher sea levels would result in increased frequency
of floods, soil loss in coastal area, sea water intrusion into rivers and other
aquatic systems near the ocean.
3) Increased CO2 levels in the atmosphere may cause plants, undergoing
photosynthesis to take up the gas at a faster rate. This may lead to faster
growth of plants in warmer climates with adequate rainfall.
4) An increase in global temperature is also likely to increase the incidence of
infectious diseases such as malaria, dengue and yellow fever.
Acid rain: Fossil fuels contain compounds of nitrogen and sulphur in addition
to carbon. Due to the combustion of these fuels, large amount of SO2, NO, NO2
and CO2, etc. get discharged into the atmosphere. The gaseous CO2 dissolves
in rain water to form weak acid, carbonic acid. At this stage, pH of water is 5.6
when the pH of rain water drops below 5.6, it becomes acidic.
CO 2 + H2O H2CO 3
+ 2-
H2CO 3 2H + CO3
However, CO2 is not the major constituent of acid rain because it is not soluble
in water compared to the oxides of sulphur and nitrogen. The oxides of
nitrogen and sulphur undergo many photochemical reactions in atmosphere
and form HNO3 and H2SO4 as described below.
NO + O3 NO 2 + O2
NO 2 + 2O2 NO 3 + O3
NO 2 + NO3 N2 O 5
N2O5 + H2O 2HNO3

On the other hand, SO2 gas formed from suphur fuels gets oxidized by NO2 to
form SO3. This gas dissolves in water droplets to form sulphuric acid.
Page 6 of 11
SO2 + NO2 SO3 + NO
SO3 + H2O H2SO4

Hence, the rain or snow falling under such conditions will contain HNO3 and
H2SO4 and becomes acidic. It is called acid rain.
Effects of acid rain:
1) Lake may become unsuitable for marine life.
2) Marble statues and buildings, often of great historic and artistic value such
as Taj Mahal get corroded.
Acid rain react with marble (CaCO3) of Taj Mahal
CaCO3 + H2SO4 CaSO4 + H2O + CO2
This causes pitting in this wonderful white monument which attracts tourists
from around the world. As a result, the Taj Mahal is being slowly eaten away. It
is also getting discoloured and luster less.
3) The soils become acidic and damage the crops
4) The Ph of the water in lakes may drop to 5. At this Ph, the acidified water
dissolves metal oxides in the soil and releases Al, Zn, Mn, and Fe. All these
metals are toxic if present in large quantity in water.
5) Acid rain dissolves heavy metals from soils, rocks and sediments. The heavy
metal ions such as Cu2+, Pb2+, Hg2+, Al3+, leached from the soil, enter well water
and produce a variety of toxic effects.
6) Acid rain also corrodes the pipes containing water supply resulting in the
leaching of heavy metals such as iron, copper and lead into the drinking water.
7) It also damages the leaves of trees and plants and retards the growth of
forests.
Photochemical smog: The term photochemical smog (combination of smoke
and fog) is used for air pollutants produced in the atmosphere as result of
photochemical reactions. Main constituents of photochemical smog are O3, NO2
and some photochemical oxidants formed by the interaction of some primary
pollutant under the influence of sunlight. Due to the presence of high
concentration of oxidants, this type of smog is oxidizing in character. Photo
chemical smog develops in cities having intense sunlight and high
concentration of automobile exhausts and stagnant air masses in the
atmosphere. Photochemical smog is formed around mid day of summer months
when the intensity of solar radiations is very high.
Mechanism of formation of photochemical smog: The combustion of
petroleum in automobile engines produces hydrocarbons as well as oxides of
nitrogen. NO2 is an effective absorber of ultraviolet rays present in sun rays.
Thus when exposed to sunlight, NO2 undergoes photolysis giving NO and O.
Through many side reactions, other pollutants like ozone, formaldehyde,
acetaldehyde, acrolein, peroxyacylnitrate (PAN) and aerosol are formed.
The oxides of nitrogen mix with smoke to form smog. The reactions
involved may be represented as
Page 7 of 11
N 2 + O2 2NO
2NO + O2 2NO2
NO 2 + h NO + O
O + O2 O3
O 3 + NO NO 2 + O2
.
RH + O RO
(hydrocarbon) .
RO . + O 2 RO 3
.
RO 3 + RH Al dehydes + ketones
RO 3. + NO .
RO 2 + NO 2
.
RO . + O
3 2 RO 2 + O 3
RO 2. + NO Peroxyacyl nitrate (PAN)
2
PAN formation can be shown by the following reaction
NO 2
H3C CH CH2 + O H3C C O O. H3C C O O NO 2
O O
PAN
Effect of photochemical smog:

1) Ozone formed during the formation of oxides of nitrogen is irritant and a
strong oxidant. It affects bean, potato, squash, tobacco and tomato plants. Of
all the components of smog PAN has the highest toxicity to plants. It attacks
younger leaves and causes bronzing and glazing of their surfaces.
2) Ozone also leads to cracking and ageing of rubber.
3) Aerosol lead to haze formation and cause reduced visibility.
4) NO2 is more toxic than NO. Breathing NO2 causes chronic lung conditions
and even death. Exposure of monkeys to 15 - 50 ppm NO2 for two hours
damage their liver, kidneys, lungs and heart. Exposure of human beings to 5
ppm, NO2 for a few minutes leads to adverse effects on their respiratory
system. It also causes fading of textile dyes and deterioration of cotton and
nylon.
Control of photochemical smog:
The best way to control photochemical smog is the installation of catalytic
converters in automobiles. Catalytic converters prevent the release of nitrogen
oxides and hydrocarbons to the atmosphere. Photochemical smog can also be
suppressed by spraying certain compounds in the atmosphere which generate
free radicals. These free radicals readily combine with free radical precursors of
photochemical smog.
Treatment of sewage: The municipal sewage consists of wastes from
residences, industries and institutions. The nature and amount of
contaminants present in sewage depend upon the habits of the residents and
the type of industries in that locality. Sewage treatment includes removal of
Page 8 of 11
suspended and dissolved wastes and microorganisms. Sewage treatment

consists of mainly three stages which are generally called primary, secondary
and tertiary treatment processes.
1) Primary treatment process: In the first stage or the primary process,
suspended particles of all kinds such as rags, paper, wires, glass, twigs, sand,
cinders, etc. are removed by passing through filters and screens of all sizes.
The waste water coming out of filters is then sent into a sedimentation tank.
The solid particles settle down. The colloidal particles are coagulated by use of
chemicals such as alum, ferric chloride and lime.
2) Secondary treatment process: The sewage water after primary treatment is
sent through trickling filters which contain rocks imbedded with biological
slime or active microorganisms. The active microorganisms are called activated
sludge and are spread as a thin layer. They thrive on organic wastes. Oxygen is
supplied as compressed air through the filters. The organic wastes present in
water undergo aerobic oxidation and biological degradation. After a few hours,
the water is run into sedimentation tanks and allowed to settle the sludge
formed is removed by filtration. Thus the function of the activated sludge is to
absorb colloidal and suspended particles if any and to bring about oxidative
degradation of organic materials in the waste water. A part of the sludge which
is rich in microorganism is used to treat the next batch of water. The other part
is dried and sold as a fertilizer. A safer and better procedure is an aerobic
digestion to yield methane (CH4).
3) Tertiary treatment process: At the end of primary and secondary sewage
treatment, most of the disease causing germs and oxygen demanding wastes
are removed. Other non degradable pollutants such as heavy metals,
pesticides, insecticides remain which need to be treated suitably according to
the pollutant present.
Chemical coagulation and filtration, chemical oxidation, carbon absorption,
ion exchange, electro dialysis and reverse osmosis are some of the methods
employed for this purpose.
Treatment of industrial effluents: Various industrial processes like
metallurgy, manufacture of paints, dyes, and drugs, paper and sugar mills and
mining discharge waste containing both inorganic and organic compounds
called industrial effluents. Some of these substances are highly toxic such as
lignin, heavy metals like Hg, Pb, Cd, Cr, As, and Ni. Since the heavy metals are
non-biodegradable, they get accumulated in the body of the living organism.
Any damage caused by these metals is usually permanent.
Though it is not possible to follow a general method for treatment of
industrial effluents because of the complexity and variety of pollutants
involved, the primary and secondary treatments used for sewage treatment is
followed by industries. The tertiary treatment however depends on the actual
pollutant present.
In paper industries, bamboo is used as a raw material. The bamboo after
chipping is washed with a large quantity of water followed by digestion in liquor
(a mixture of NaOH and Na2SO4) to obtained pulp. The effluent contains
dissolved lignin, cellulose fibers, greases, oils, alkalis, heavy and other metals,
Page 9 of 11
organic compounds and is called black liquor. At least 50% of the wood used
as input is discharged into waste.
The colour of the effluent is removed by treatment with lime. The black liquor is
neutralized with acid when lignin gets separated. The insoluble material is
removed by filtration.
The remaining chemicals are removed by
1) Activated sludge process by oxidation with chlorine.
2) By ultra filtration or reverse osmosis.
In sugar industries, the effluents contain wastes of high biochemical
oxygen demand including sugar and proteins. This is subjected to oxidation
where the microorganism oxidizes them to alcohol, CO2 and CH4.
Disposal of radioactive wastes: Spent nuclear fuel mainly consists of a
mixture of uranium, plutonium and fission products. Since the heat generated
by the decaying fission products is too high during the first one or two years,
spent fuel is generally stored mainly in deep, water filled pools at the reactor
sites to cool them and shield their radiation. However, this is only a short term
solution. Eventually, a long term solution is required. Some of the methods
used are:
a) Use of multiple barrier system: For the disposal of nuclear wastes on long
term basis, the spent fuel is packed into containers made up of corrosion
resistant material such as titanium, nickel or copper alloys. The sealed
containers are then placed in caverns drilled in a geologically stable graphite
rock filled and plugged so that no further supervision is needed.
2) Disposal into underground salt domes: In this type of technique, the
sealed containers containing spent nuclear fuel are buried into the deep
underground salt domes.
3) Disposal into deep sea beds: Another method tried for the disposal of
nuclear wastes is the placement of nuclear waste into the deep sea bed.
4) Disposal into the solid matrices: In this method, nuclear waste is packed
into borosilicate glass or ceramic matrix and then placed in suitably designed
and constructed underground repositories that remain free from seismic and
any other disruptive activities.
OR
(One of the major problems of the development of nuclear reactors and use of
nuclear energy is the disposal wastes. Many fission products such as Ba - 140,
Kr 85, Sr- 90, Cs 137 have very long lives and harmful to human and other
living beings. Pu 239 produced in a breeder reactor and used as a nuclear
fuel is one of the most toxic substances known with a very long half- life of
24,400 years.
The disposal of radioactive wastes needs a special treatment unlike other
wastes as their radioactivity cannot be reduced by any chemical treatment.
The radioactive wastes after reprocessing are disposed off depending upon
their physical state.
The solid wastes are stored in thick leak proof shielded steel tanks and
buried deep underground or beneath ocean floor.
Page 10 of 11
The liquid wastes are discharged into dry wells containing soil associated
with synthetic aluminosilicates which serve as ion exchangers. These materials
are cheap and are not affected by heat and radiation.
The gaseous wastes of a short life period can be disposed off by diluting with
excess of air and slowly releases into the atmosphere through high stacks.
Those with long half lives are absorbed on activated carbon or silica gel and
then buried deep underground).
Terminology (Not for syllabus)

1) Pollutant: If the concentration of a substance already present in nature is
increased to undesirable proportion by human action, so that, it spoils the
environment and reduces quality of the life or affects health then it is called as
pollutant.
2) Contaminant: A substance that does not occur in nature but is introduced
in significant amounts into the environment by human action is known as a
contaminant. A contaminant also reduces quality of life and affects our health.
3) Receptor: It is an element or organism affected by a pollutant. For example,
human being is the receptor of smog as it causes irritation in eyes and
breathing problems.
4) Sink: The element or surroundings that interact and consume a long lived
pollutant is known as a sink. A marble deposit acts as a sink for atmospheric
acid and in the process gets damaged.
5) Dissolved oxygen (DO): It is an important parameter to determine water
quality because it is vital for aquatic life. The optimum value for good quality is
4 -6 mg/ lit of DO. Lower Do values indicate polluted water unfit for human or
aquatic consumption.
6) Biological oxygen demand (BOD): The capacity of the organic matter in the
sample of natural water to consume oxygen is called its BOD. It is evaluated
experimentally by determining dissolved O2 At the beginning and at the end of
a 5 day period in a sealed sample. The BOD equals the amount of oxygen
consumed in the period as a result of the oxidation of dissolved organic matter
in the sample.
7) Chemical oxygen demand (COD): This is an important water quality
parameter. It is index of the organic content of water because the most
common substance oxidized by dissolved oxygen in water is organic matter
having a biological origin, such as dead plant and animal waste. Dissolved
oxygen in water is also consumed to some slight extent for oxidation of
inorganic matter such as dissolved ammonia, and ammonium salts into
nitrates. COD is determined with the help of acidified dichromate solution.
Page 11 of 11

Chapter 5 Organic Spectroscopy.

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Chapter 5 Organic Spectroscopy.

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V Semester (organic) notes prepared by Dhondiba V.Suryawanshi, GCW Kolar.

Chapter 5: Spectroscopy of Organic compounds 8 hours

UV-Visible spectroscopy: Introduction. Chromophores and auxochormes; blue

IR spectroscopy: Introduction. Stretching frequencies of OH (free and H-

NMR spectroscopy: Basic principles of proton magnetic resonance: Nuclear

Applications of NMR spectroscopy including identification of simple organic

Electromagnetic Radiation Interact with Matter (Atoms, Molecules) =

visible spectroscopy. These radiations having the sufficient energy to

1) * transitions: This type of transition involved in the saturated

2) n * transition: This type of transition involved in the saturated

n *. But this type of transitions gives the absorption band at near

3) * transition: This type of transition involved in the unsaturated

* absorption peaks are observed. This type of transition depends on

4) n * transition: This type of transition involved in the unsaturated

Chromophores: Any multiple bonded group which exhibits absorption of

Auxochromes: A saturated group which itself does not act as a chromophore

longer wavelength along with an increase in the intensity of absorption called

benzene phenol aniline

Hypsochromic shift (blue shift): A shift of max absorption to a lower (short)

Influence of conjugation on max absorption: Conjugation of double bands

As a result CH=CH-CH=C and CH=CH- C=O exhibit *

They involved * and n * are takes place. * transition

UV-Visible spectra of acetone

180 280 320

Now, the vinyl methyl ketone is conjugated molecule of acetone. Due to

max = 219 nm and max = 3600

n max = 324 nm and max = 24

The graphical representation of methyl vinyl ketone is given below.

UV-Visible spectra of methyl vinyl ketone

due to max 324 nm

200 260 380

Also, compounds in which the carbon-oxygen double bond is conjugated with a

max = 219 nm and max = 3600

n max = 324 nm and max = 24

Graphical representation UV-Visible spectra of 1, 3- butadiene:

In buta-1, 3-diene, CH2=CH-CH=CH2, there are no non-bonding electrons. That

Graphical representation UV-Visible spectra of benzene: Benzene is a

Absorbance max = 256 nm

200 220 240 260 280 300 320

Graphical representation UV-Visible spectra of lycopene: Structure of

It contains highly conjugated pi bond system. Hence it absorbs electromagnetic

200 250 300 350 400 450 500 550

Absorption by Compounds with C=O Bonds

Aldehydesand ketones have two absorption bands in the ultraviolet region.

Introduction: The technique which is used to determine the structure of

Wave number is the reciprocal of wavelength. Band intensities in IR spectrum

Conditions for a molecule to give IR spectrum OR conditions for a

Stretching and bending modes of vibrations: The atoms containing a

Types of stretching vibrations: In tri atomic or higher molecules, the

Types of bending vibrations:

= Reduced mass of diatomic

2) Fingerprint region: Absorbance bands of the health observed in the range

2700 -2800 C H (of aldehyde group)

Graphical representation of IR spectra of benzoic acid:

Note: On Y axis = Transmittance and on X axis = wave number

Benzoic acid (C6H5COOH)

(3230-3550) O-H stretch Broad Absorption due to H bonding between

(2840-3000) C-H stretch

(1400-1500) C=C aromatic stretch

(1000-1300) C-O stretch

(1680-1740) C=O stretch

Nuclear magnetic resonance spectroscopy:

Introduction: The technique which is used to determine the structure of

[Nuclear Magnetic Resonance (NMR) Spectroscopy involves the absorption of