BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Semester I: AY 2017-18
Lecture-15, 06-09-2017
BITS Pilani, Pilani Campus
 Notice
TUTORIAL SECTION 4 TUTORIAL SECTION 7
DATE: Wednesday 6th Sep 2017 DATE: Wednesday 6th Sep 2017
Instructor: Ajay K. Sah Instructor: Saumi Ray
TIME: 5.00pm TIME: 5.00pm
VENUE: Room No. 3252 VENUE: Room No. 3249
...................................................................
TUTORIAL SECTION 8

DATE: Thursday 7th Sep 2017

Instructor: Madhushree Sarkar
TIME: 5.00pm
VENUE: Room No. 3248
BITS Pilani, Pilani Campus
 Academic Counseling Cell (ACC)
BITS, Pilani (Pilani Campus)

Know your Professors better ..

Also, to all those talented First Year students who did not get a
chance to perform in any event so far, do not be disheartened-
you can perform at:

Koffee with Profs"

(A fun interaction between faculty and students)

An event organized by ACC

Date: 8th September 2016, Friday, Time: 5:15 PM
Venue: Rotunda

If you have an item (group song, skit, dance, etc) ready and
would like to perform, please call 823972399 after 5pm today or
latest before 8pm on 6th August.
Raman Spectroscopy - explanation
+ ve - ve
This separation of charge
centers caused an
- ve + ve induced electric dipole
moment

Molecule is polarized
Polarization leads to dipole moment in the molecule
induced dipole moment
Induced dipole: = ; :
is a parameter the ease with which a molecule can be distorted -
polarizability BITS Pilani, Pilani Campus
Raman Spectroscopy selection rule
Some internal motion of the molecule, such as, rotation and/or

vibration must change the polarizability, i.e., 0

q represents the coordinate in terms of the internal motion

If molecular rotation/vibration causes some change in

molecular polarizability then those rotation/vibration must be
Raman Active
Conditions imposed on rotation model we have used:
Molecules must be non-rigid and hence polarizable
BITS Pilani, Pilani Campus
Pure rotational Raman Spectroscopy
Polarizability: Bonds must be non-rigid.
For practical purposes (limited resolution) we may not obtain any
information about the distortion of the molecules.
Thus, we can start with = + 1 1 , = 0, 1, 2, . . . .
Selection rule: = 0 2 only
= 0 Trivial transition, represents Rayleigh scattering.

= +2 = 4 + 6 1

1
= +2 = 4 + 6
BITS Pilani, Pilani Campus
Pure rotational Raman Spectroscopy
1
=
4 + 6
1

=
+ 4 + 6

BITS Pilani, Pilani Campus

Rotational Raman spectrum of CO2
Homonuclear diatomics:
H2, O2, N2: Rotationally
inactive
Active in rotational
Raman
Raman spectroscopy
provide information
about the structure

BITS Pilani, Pilani Campus

Vibrational spectroscopy
1 1
Diatomic molecule: A-B = 2 = ( )2
2 2
K: force constant with dimension N m-1
In the harmonic approximation:
1
= + ; = 0, 1, 2, . . .
2
1
= ; =
2 +

In terms of wave number:

1
= + , = 0, 1, 2, . . .
2
BITS Pilani, Pilani Campus
Vibrational spectroscopy selection rules
Vibrational transitions: At frequencies of 1013 to 1014 Hz, infrared spectroscopy.
|2
Transition probability |
Gross selection rule: The electric dipole moment of the molecule must

change during the vibration,

Specific selection rule: =
E = h
Most important transition from = 0 to = 1.
Homonuclear diatomics are IR inactive as Rotational inactive
BITS Pilani, Pilani Campus
Vibrational spectroscopy
A single oxygen atom is attached to a smooth metal surface. The atom vibrates
at a frequency of 1.80 X 1013 s-1. Calculate its total energy for n = 0, 1, and 2
quantum no. states.
E (n=0) = 5.963 X 10-21 J
E (n=1) = 1.789 X 10-20 J
E (n=2) = 2.982 X 10-20 J
Calculate the wavelength of light necessary to excite a harmonic oscillator from
one energy state to the adjacent state in the previous example.

16.66
BITS Pilani, Pilani Campus
Anharmonicity
We obtain overtones as well

Fragmentation
channel
Additional weak transitions:
= 2, 3, etc for anharmonic
oscillator

Anharmonicity:
Can not break or make a bond E = ( + )hc - ( + )2 hc xe + .
- Chemistry could be at danger xe is anharmonicity constant
BITS Pilani, Pilani Campus
Vibrational spectra: Polyatomic molecules
Degrees of freedom
For a molecule with N
atoms, the number of
coordinates required to
specify the position of
all the atoms is 3N.
These 3N
displacements can be
thought of in terms of
Translational : 3 various degrees of
freedom.
Rotational : 2 for linear and 3 for nonlinear molecule
Vibrational : 3N 5 for linear and 3N 6 for nonlinear molecule.
BITS Pilani, Pilani Campus
Normal modes of vibrations
Description of vibration most convenient and simple in terms of
normal modes.
Normal mode Collective, independent, synchronous motion of
group of atoms, that may be excited without exciting any other
mode.
Each normal mode may be approximated as a harmonic oscillator
with a characteristic frequency and an effective mass.
Any arbitrary displacement may be expressed as a superposition of
the normal modes.
BITS Pilani, Pilani Campus
Vibrational spectroscopy

Actual (total) stretching motion

Independent components
contributing to the motion (Normal
modes): symmetric and asymetric
stretching

BITS Pilani, Pilani Campus

Water: Normal modes of vibrations

Symmetric Asymmetric
stretch Bend stretch

BITS Pilani, Pilani Campus

Carbon dioxide: Normal modes of vibrations

Symmetric stretch IR inactive

Bend

Bend

Asymmetric stretch
BITS Pilani, Pilani Campus
Vibrational spectroscopy
Infrared spectroscopy powerful tool in
identifying organic molecules.
Some modes essentially motions of individual
functional groups.
Others are collective motions of the molecule
as a whole fingerprint region of spectrum.

BITS Pilani, Pilani Campus

Vibrational (IR) spectroscopy
Absorption frequency:
= 1/2 (k/1/2 where = mAmB/(mA + mB) is the reduced mass and k is force
constant

Typical range : 1013 1014 Hz ~ 102 103 cm-1 (Infrared region)

Hence, vibrational (absorption) spectroscopy is also known as IR spectroscopy.

{IR spectrum is generally represented in Transmission mode}

BITS Pilani, Pilani Campus
IR frequency calculation
Absorption frequency:
(cm-1) = (k/1/2 /2c

C-H: k ~ 494 Nm-1; (~ 3000 cm-1)

N-H: k ~ 642 Nm-1; (~ 3400 cm-1)

O-H: k ~ 726 Nm-1; (~ 3600 cm-1)

C=C: k ~ 972 Nm-1; (~ 1650 cm-1)

CC: k ~ 1650 Nm-1; (~ 2150 cm-1)

BITS Pilani, Pilani Campus

IR frequencies of functional groups

Here the effect is mainly

due to bond strength

BITS Pilani, Pilani Campus

Factors affecting absorption frequency
Absorption frequency:
Increases with increase in % of s character: sp3<sp2 <sp
e.g. C-H stretching frequencies:
< 3000 cm-1 for sp3, >3000 cm-1 for sp2, ~3300 cm-1 for sp
Decreases on increase in conjugation
e.g. In aldehydes, ketones and esters, C=O stretching
frequency decreases by 25~30 cm-1 when conjugated with
C=C
Is affected by inductive/resonance/electromeric effects
Decreases due to hydrogen bonding
BITS Pilani, Pilani Campus
Interpreting IR spectra
O C=O at 1725 cm-1 O C=O at 1710 cm-1
R C also look for aldehyde CH R C also look for OH
(H-bonded) and
H 2850 and 2750 cm-1 O H C-O ~1200 cm-1

O C=O at 1690 cm-1 O C=O at 1735 cm-1

R C R C also look for two
N H also look for two
NH peaks at O R' C-O at 1200 and
H 3400 cm-1 1000 cm-1

Ketones have C=O at 1715 cm-1 and no NH, OH, C-O or -CHO
Anhydrides have two C=O peaks near 1800 cm-1 and two C-O

BITS Pilani, Pilani Campus

Carbon dioxide: Normal modes of vibrations

Symmetric stretch IR inactive

Why??
Bend

Bend
=

Asymmetric stretch
BITS Pilani, Pilani Campus
Methane: Normal modes of vibrations

BITS Pilani, Pilani Campus

IR frequency data

BITS Pilani, Pilani Campus

IR frequency data

BITS Pilani, Pilani Campus

Interpreting IR spectra
C-H stretching frequencies:
<3000 cm-1 for sp3; >3000 cm-1 for sp2; ~3300 cm-1 for sp3;
Methylene and methyl C-H stretching: ~2850 cm-1 (sym); ~2950 cm-1 (asym)

Hexane

BITS Pilani, Pilani Campus

Interpreting IR spectra
Toluene: Ar-H, CH2-H, C=C

CH3
C=C
benzene

BITS Pilani, Pilani Campus

Interpreting IR spectra
O-H stretching: ~3600 cm-1 for alcohols;
brodens and lowers to 3300 cm-1 due to H-bonding in alcohols, acids, etc.
How to distinguish between intramolecular and intermolecular H-bonding?

O-H OH CH2
H-bond
C-O

C-H

BITS Pilani, Pilani Campus

Interpreting IR spectra
C=O is highly sensitive to its environment

EACH DIFFERENT KIND OF C=O COMES AT A DIFFERENT FREQUENCY

acid carboxylic
chloride ester aldehyde ketone acid amide
O O O O O O
RC RC RC RC RC RC
Cl OR
' H R OH N
H2
1800 1735 1725 1715 1710 1690

anhydride
O O BASE
VALUE
RCOCR

1810 and 1760 THESE VALUES ARE

WORTH LEARNING

BITS Pilani, Pilani Campus

Diatomic vibrating rotor

BITS Pilani, Pilani Campus

Diatomic vibrating rotor
rotor: CO

BITS Pilani, Pilani Campus