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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V Semester (organic) notes prepared by Dhondiba V.Suryawanshi, GCW Kolar.
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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Energy
n
n - n-
-N = N - -N=O -N=O
Diazo Nitroso Nitro
p - quinone o - quinone
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aniline anilinium
max = 280 nm max = 250 nm
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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
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
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due to n
due to
wavelength in nm
H2C CH C CH3
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max 219 nm
due to n
wavelength in nm
H2C CH C CH3
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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".
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CH3
CH3 CH3 CH3
CH3
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max = 471nm
Lycopene
Lycopene
Absorbance
H3C
..
C O max187 nm
..
H3C
n * max nm
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max nm
max187 nm
n n
Excited state Excited state
n
Ground state
H3C
..
C O
..
H3C
Infrared spectroscopy
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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 =
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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
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,
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.
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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 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.
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.
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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.]
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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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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.
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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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.
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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.
10 9 8 7 6 5 4 3 1 0
2
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
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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:
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TMS
Singlet
1HNMR of CH4
10 9 8 7 6 5 4 3 2 1 0
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TMS
Singlet
1HNMR of CH3Cl
10 9 8 7 6 5 4 3 2 1 0
TMS
1HNMR of CH2Cl2
Singlet
10 9 8 7 6 5 4 3 2 1 0
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TMS
1HNMR of CHCl3
Singlet
10 9 8 7 6 5 4 3 2 1 0
2 1 TMS
1HNMR of Cl2CHCHO
Doublet Doublet
Cl2CH- -CHO
J J
10 9 8 7 6 5 4 3 2 1 0
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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
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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.
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
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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.
2 1 TMS
1HNMR of ClCH2CH3 quartet
ClCH2-
triplet
-CH3
J
J
10 9 8 7 6 5 4 3 2 1 0
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, ,
, ,
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:
, ,
, ,
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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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
UNIT IV
Aliphatic Hydrocarbons
9 hours: Max. Marks: 18 -20
Syllabus:
Aliphatic hydrocarbons: A branch of organic chemistry which deals with study of open
chain compounds containing carbon and hydrogen as elements called aliphatic hydrocarbons.
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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
1) Natural gas contains about 80% methane and 10% ethane, the remaining 10% being a
mixture of higher members.
3) Plant waxes also contain saturated hydrocarbons having odd number of carbon atoms (C27
to C37). Bee wax contains C27H56 and C31H64.
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.
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.
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
Isobutane Isopentane
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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).
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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
1) Name the longest chain: The longest continuous carbon chain is chosen as the basic for
the name and it written in horizontal fashion.
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) 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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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) This method is satisfactorily explained to prepare higher alkanes from the lower alkyl
halides.
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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
2Li CuI
R-X R - Li (R) 2CuLi
- LiX
Alkyl halide Ethyl lithium Lithium dialkyl 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.
H
H H H
H H H
H H H
H H
H
H CH 3
Ethane
Propane n - Butane
Staggered conformations
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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).
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
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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).
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.
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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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) 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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
O
O
CH2 C Clemmensen reduction
H2C O
Zn or Hg
Ca
- CaCO 3 HCl
H2C CH2 C O
cyclopentane
cyclopentanone
O
Calcium adipate
Clemenmensen reduction
O
- CO 2 Zn or Hg / HCl
Cyclopentane
pentanone
Ni,
+ 3H2
Pressure
Benzene Cyclohexane
Stability of cycloalkanes:
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
Stability increases
Page 12 of 35
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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.
5 (109028 - 1080) = 00 44
0
108
Page 13 of 35
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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.
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.
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
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
R1 R1
R2 Triphenylphosphine oxid
R2 Triphenylphosphine- methylene
Aldehydes Alkenes
(or ketones)
Where, R1 = R2 = H or alkyl group
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
H3C
H3C
C O + H2C = P(C6H5)3 H3C C CH2 + (C 6H5)3P = O
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
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
Properties of alkenes:
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%)
Propene Br
2 - bromopropane
(80%)
1) Formation of a carbo-cation. Notice that for alkene, two carbo-cations are possible.
Page 17 of 35
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
+ -
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
Peroxide (R - O - 0 - R)
R CH CH2 + HX R CH2 CH2 X
Unsymmetrical
1 - haloalkane
alkene
(20%)
(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.
.
R O O R 2R - O
Peroxide radical
Peroxide
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
. .
R-O + H Br R OH + Br
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
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:
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
H2O 2 / Base
3CH3 - CH 2 - CH 2 - OH + B(OH) 3
Oxidation
1 - Propanol
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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
Oxymurcuration:
OH
Hg(O - CO -CH 3)2
R CH CH2 R CH CH2
H 2O
O
Oxymercuration product
Demercuration:
OH
OH
R CH CH2 Reduction
R CH CH3 + HgOH C CH3
OHg C CH3 NaBH4
Alcohol O
O
Oxymercuration product
Oxymercuration:
OH
Hg(O - CO -CH 3)2
H3C CH CH2 H3C CH CH2
H2O
- CH 3COOH OHg C CH3
Propene
O
Oxymercuration product
Demercuration:
OH
OH
H3C CH CH2 Reduction
H3C CH CH3 + HgOH C CH3
OHg C CH3 NaBH4
2 - Propanol O
O
Oxymercuration product
4) Epoxidation of alkenes: Alkenes react with oxygen gas in presence silver catalyst at 250 -
4000C to from epoxide.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
O
Ag
R CH CH2 + O2 R HC CH2 + AgO
Alkene Epoxide
For example,
O
Ag
H3C CH CH2 + O2 H3C HC CH2 + AgO
Propene Propylen epoxide
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
Intermediate complex
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
Intermediate complex
H H
Ethene O - O OH OH
[O] Os
H C C H
OsO 4 in pyridine O O
H H H H
C C
Ethylene glycol
H H
Intermediate complex
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
2, 3 - dimethyl 2 -butene O O
- OH OH
[O] Os
H3C C C CH3
OsO 4 in pyridine O O
H3C CH3 CH3 CH3
C C
2,3 - dimethybutan 2,3 - diol
H3C CH3
Intermediate complex
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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
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)
V
3O2 2O3
High voltage
Oxygen gas Ozone
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
+
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
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
-
+ 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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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:
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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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)
SP 2
H -S
2 -S
2
SP - SP 2
SP2 - SP2 SP H
C C
C
H H
H H
C C C
H
H
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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
H H
H H
C1 C2 C4
H C2
C3 C4 C1 C3 H
H
H H Partial double bond
H
Page 28 of 35
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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)
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.
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
+ 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)
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)
O O
CH2 0
100 C
+ O O
CH2
O O
1, 3 -Butadiene Maleic anhydride
(Diene) (Dienophile) (Adduct)
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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:
2 HC CH Acetylene (ethene)
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
This method is useful method since the vicinal dihalides are readily prepared from alkenes by
the addition of halogens.
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
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I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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)
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
H Br H Br
KOH in alcohol KOH in alcohol
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
KOH in alcohol KOH in alcohol
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
Page 32 of 35
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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
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
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
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
1 KMnO4 1
R C C R + 4[O] R COOH + R COOH
Base
Alkyne Carboxylic acid Carboxylic acid
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
= 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
I SEMESTER B. Sc. NOTES PREPARED BY DHONDIBA VISHWANATH SURYAWANSHI (DVS) GCW, KOLAR
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.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
= . (2)
Where, g is acceleration of gravity, h is height from ground and is density of
liquid.
4
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
= . (4)
Divide equation (3) by (4) finally we get,
6
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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.
7
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
+ pB B1
Vapour pressure
P = pA
Vapour pressure
0
1 pA
A = XA
pA
pA =
XB p 0
B
8
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
= = = =
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 +
9
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
2) Type II non ideal solution: The solution of type II show large positive
deviations from ideal behavior, the vapour pressure of each component being
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
10
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
3) Type III non ideal solution: The solution of type III show large negative
deviations from ideal behavior, the vapour pressure of each component being
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
A = acetone B = Chloroform
11
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
Mole fraction Mole fraction
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
Mole fraction Mole fraction
B=0 A=0 B=0 A=0
13
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
Then the ratio of the number of moles of liquid phase to the number of moles of
vapour phase is given by
V
TA0
v V+L
a* l
TB0 L
A=0 A=1
B=1 B=0
14
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
15
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
UCST
Temperature in 0C
68.1
0 36.1 100
of phenol
Phenol - water system
Two phases
18.5
LCST One phase
0 100
of Triethylamine
Triethylamine - water system
16
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
Temperature in 0C
Two phases
60
LCST One phase
0 100
of Nicotine
Nicotine - water system
17
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
i. e. Where,
18
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
2) It is used to study the dissociation of a solute by using the equation
20
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
[ ]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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
*
*
Equilibrium pressure
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
And
Where, M is the molecular mass of solvent.
25
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
And
26
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
28
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
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
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
Ax By xAy+ + yBx-
1- nn
This equation is used to calculate the degree of dissociation of an electrolyte.
Problems:
30
I semester B.Sc. notes prepared by Dhondiba V. Suryawanshi, GCW Kolar.
31
IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
Page 1 of 11
IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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)
Page 2 of 11
IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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
IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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
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IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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
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IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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
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IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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
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IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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.
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IV SEMESTER B.Sc. CHEMISTRY 7-ENVIRONMENTAL CHEMISTRY
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).
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