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Infrared Spectroscopy RC

Here are the key steps: - The original compound has peaks at 3580, 2890, 1260 cm-1 - 3580 cm-1 is characteristic of O-H stretch - 2890 cm-1 is characteristic of C-H stretch - 1260 cm-1 is characteristic of C-O stretch - This matches ethanol (C2H5OH), which has an O-H group - When treated with SOCl2 or PCl5, the O-H is replaced by Cl, forming C2H5Cl - Therefore, the original compound was ethanol, which reacts to form ethyl chloride upon treatment with SOCl2 or PCl5 The original compound was ethanol

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111 views22 pages

Infrared Spectroscopy RC

Here are the key steps: - The original compound has peaks at 3580, 2890, 1260 cm-1 - 3580 cm-1 is characteristic of O-H stretch - 2890 cm-1 is characteristic of C-H stretch - 1260 cm-1 is characteristic of C-O stretch - This matches ethanol (C2H5OH), which has an O-H group - When treated with SOCl2 or PCl5, the O-H is replaced by Cl, forming C2H5Cl - Therefore, the original compound was ethanol, which reacts to form ethyl chloride upon treatment with SOCl2 or PCl5 The original compound was ethanol

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Sricharan
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Infrared Spectroscopy

 Energy Quantization
 Energy Quantization refers to the absorption or
emission of energies in discrete packets, or quanta.

 As the intensity of the electromagnetic radiation


increases or decreases, it steps up or down from one
quantized level to another, rather than follow a smooth
or continuous curve.
 Born–Oppenheimer approximation
 In quantum chemistry and molecular physics, the Born–
Oppenheimer (BO) approximation is the assumption that the
motion of atomic nuclei and electrons in a molecule can be
treated separately
 In molecular spectroscopy, using the BO approximation means the
total energy of the molecule (molecular energy) in the gas or
liquid phase is a sum of independent energies such as electronic,
vibrational and rotational energies. Translational energy of the
molecule can be neglected.
 The electronic energy consists of kinetic energies, interelectronic
repulsions, internuclear repulsions, and electron–nuclear
attractions, which are the terms typically included when
computing the electronic structure of molecules.
Wavelength increases, Energy decreases
 Franck–Condon principle
 The Franck–Condon principle is a rule in spectroscopy and
quantum chemistry that explains the intensity of vibronic
transitions. Vibronic transitions are simultaneous changes in
electronic and vibrational energy levels of a molecule due to the
absorption or emission of a photon of the appropriate energy.
 The principle states that during an electronic transition, a change
from one vibrational energy level to another will be more likely to
happen if the two vibrational wave functions overlap more
significantly.
Infrared Radiation
 Electromagnetic radiation longer than the red end of the visible
light and shorter than the microwaves (roughly between 1 to 100
microns).

 Almost none of the infrared portion of the electromagnetic


spectrum can reach the surface of the Earth.

 Conditions for IR active


 For a molecule to be infrared active, the dipole moment of the
molecule must change during the vibration.

 Homonuclear diatomic molecules such as hydrogen (H2), Nitrogen


(N2), and Oxygen (O2) are IR inactive because of the change in the
dipole moment in these molecules even after irradiation with IR
radiation is zero.
Fourier Transform Infrared (FT-IR)
 FT-IR is a molecular spectroscopy
which is used to characterize
both organic and inorganic
functional groups.
 The sample is irradiated with
infrared radiation.
 When the frequency of the IR
radiation matches the natural
frequency of the bond, the
amplitude of the vibration
increases, and the infrared is
absorbed.
 The output of an infrared
spectrophotometer is a chart
with %T vs cm-1
 Hooke’s Law

• To help understand IR, it is useful to compare a


vibrating bond to the physical model of a vibrating
spring system.
• The spring system can be described by Hooke's Law
shown below.
1 𝑘 𝑚1 𝑚2
ῡ= R𝑒𝑑𝑢𝑐𝑒𝑑 𝑀𝑎𝑠𝑠 = μ =
2π𝑐 μ 𝑚1 + 𝑚2
• Consider a bond and the connected atoms to be a
spring with two masses attached.

• Using the force constant k (which reflects the


stiffness of the spring) and the two masses m1
and m2, then the equation indicates how the
wavenumber, ῡ, of the absorption should change
as the properties of the system change.
Consider the following trends:
1. for a stronger bond (larger k value), n increases.
As examples of this, in order of increasing bond strength compare:
CC bonds:
C-C (1000 cm-1), C=C (1600 cm-1) and C≡C (2200 cm-1),
CH bonds:
C-C-H (2900 cm-1), C=C-H (3100 cm-1) and C≡C-H (3300 cm-1),
(n.b. make sure that you understand the bond strengths order)

2. for heavier atoms attached (larger m value), n decreases.

As examples of this, in order of increasing reduced mass compare:


C-H (3000 cm-1)
C-C (1000 cm-1)
C-Cl (800 cm-1)
C-Br (550 cm-1)
C-I (~ 500 cm-1)
Problem: Calculate the vibrational absorption (in
wavenumber) of carbonyl group, if K (force
constant) for double bond is 1 × 106 dynes/cm.
1 𝑘
ῡ=
2π𝑐 μ
𝑚1 𝑚2
R𝑒𝑑𝑢𝑐𝑒𝑑 𝑀𝑎𝑠𝑠 = μ =
𝑚1 + 𝑚2

16 𝑔
Mass of oxygen = m1 = = 2.66 × 10−23 𝑔
6.023 × 1023

12 𝑔
Mass of carbon = m2 = = 1.99 × 10−23 𝑔
6.023 × 1023

𝑚1 𝑚2 2.66 × 10−23 𝑔 ×(1.99 × 10−23 𝑔) (5.2934 × 10−46 𝑔2 )


Reduced mass = μ = = = = 1.14 × 10−23 g
𝑚1 +𝑚2 (2.66 × 10−23 𝑔 +1.99 × 10−23 𝑔) (4.65 × 10−23 𝑔)

1 𝑘 1 1 × 106 𝑑𝑦𝑛𝑒𝑐𝑚−1 1 × 106 (𝑔𝑐𝑚𝑠 −2 )𝑐𝑚−1


ῡ= = = 0.0531 × 10−10 𝑐𝑚−1 𝑠 ×
2π𝑐 μ 2 3.14 (3 × 1010 𝑐𝑚𝑠 −1 ) 1.14 × 10−23 g 1.14 × 10−23 g

(1 dyne = 1gcm/𝑠 2 )
= 0.0531 × 10−10 𝑐𝑚−1 𝑠 × 2.962 × 1014 𝑠 −1
= 1572.8 cm-1
Problem: Calculate the approximate vibrational
absorption (in wavenumber) of C-H stretching in
methyl group, if K (force constant) for single bond is
5 × 105 dynes/cm. The masses of “C” and “H” are 2 ×
10-23 g and 0.167 × 10-23 g respectively.

Practice at Home
A compound with MF C2H6O has given IR signals/peaks at
3580 cm-1, 2890 cm-1 and 1260 cm-1. When the same
compound is treated with SOCl2 or PCl5 gave a compound
of MF C2H5Cl. Identify the compound.

Hints:
OH, CH and CO Stretching vibrations are observed

2 possibilities: ethanol and diethyl ether

Practice at Home

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