Chapter 5

Absorption Spectroscopy:
There are three common types of
transitions:

❑Rotational transition: the molecule rotates

about various axis. Molecule absorbs radiation
and is raised to higher rotational energy level.
❑Vibrational transition: the molecule absorbs
a discrete amount of energy and is raised to
higher vibrational energy level.
❑Electronic transition: the electrons of a
molecule may be raised to a higher electron
energy level.

❖ The relative energy levels of the three Energy levels for a molecule. Possible transitions
transition processes are in the order: that occur:
(A) Pure rotational Transitions (lines)
(B) rotational-Vibrational Transitions (sharp band
electronic > vibrational > rotational.
or peak)
(C) Rotational-Vibrational-Electronic Transitions
(broad band)
 IR region:
• The near IR (NIR): it is the higher-energy near-IR, lying
adjacent to the visible region approximately 12500–
4000 cm−1 (0.8–2.5 μm wavelength).

• Mid- IR: approximately 4000–400 cm−1 (2.5–25 μm) may

be used to study the fundamental vibrations and associated
rotational-vibrational structure. It is called also NaCl-IR
region

• Far- infrared: approximately 400–40 cm−1 (25-250 μm),

lying adjacent to the microwave region, has low energy and
may be used for rotational spectroscopy.
Wavenumber is the reciprocal of this wavelength
͞ν = 1/λ (cm-1 )

Example : Calculate the wavenumber in cm-1 for

the wavelength λ = 0.70 μm.
Ans.

1 106μm 1m
͞ν = x x
0.70 μm 1m 102 cm

= 1.43 x 104 cm-1

 Absorption Spectroscopy:
G.R: IR technique is
suitable for qualitative
analysis
specific transitions for
certain functional
No qualitative applications as high groups (limited
interferences of many electronic transitions in interferences)
the molecule

IR spectroscopy is still band spectra not line spectra as the

atomic spectroscopy
G.R: The vibrational spectra appear as bands rather than lines.
band spectra. The single vibrational energy change
(vibrational transitions) is accompanied by a number of
rotational energy changes.–> “vibrational-rotational bands”
• An IR spectrum is essentially a graph of infrared light
absorption or transmittance on the vertical axis versus the
frequency or wavenumber on the horizontal axis.
• Typical units of frequency used in IR spectra are
wavenumbers, cm−1.
• When Infrared radiation is absorbed by molecules it is
converted into energy of molecular vibration

Hooke's law

1 𝑘
νത =
2𝜋𝑐 μ
k : force constant . its values depends on the strength of the bond
as follows:
single bond 5 x 105 dyne/cm
double bond 10 x 105 dyne/cm • Example: Kcc > K c=c > Kc-c
triple bond 15 x 105 dyne/cm
The vibrational frequency is increasing with (TWO factors) :
▪ increasing force constant k = increasing bond strength
▪ decreasing atomic mass
 1 𝑘 ν̅1 μ2
νത = =
2𝜋𝑐 μ ν̅2 μ1

𝑚1 .𝑚2
μ= (reduced mass)
𝑚1 +𝑚2

𝐴𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡
𝑚=
𝑁𝐴

𝐴𝑡𝑊𝑡1 .𝐴𝑡𝑊𝑡2
μ= (reduced mass)
(𝐴𝑡𝑊𝑡1 +𝐴𝑡𝑊𝑡2 )𝑁𝐴
Example:: Calculate the fundamental frequency expected in the IR absorption spectrum
for the C-O stretching frequency.
The value of the force constant is 5.0 x 105 dynes cm-1.
Answer:
1
͞ν (in cm-1 ) = 10 (5.0 x105) 12 + 16 (6.023 𝑥1023 )/(12)(16)
(2)(3.14)(3 x10 )

= 1307 (5.0)(12 + 16)/(12)(16)

= 1110 cm-1
m1 = 12 / 6.023 𝑥1023 and m2 = 16 / 6.023 𝑥1023

• As the mass of the atoms increases, the vibration frequency decreases.

Using the following mass values: C, carbon 12/6.02 x 1023 and H,
hydrogen 1/6.02 x 1023

For a C–H bond, is calculated to be 3029 cm–1 (Try this calculation!).

 Problems on IR:
1- Calculate the approximate wave number of vibrations and
the wavelength of the fundamental absorption peak due to the
stretching vibration of C=O, where the force constant equals 1
x 106 dyne/cm, avogadro’s number = 6.023 x 1023 .
Ans. 1572 cm-1

2- The frequency of C12-O16 stretching in C=O is 1572 cm-1,

Predict the frequency of the same molecule when C12 is
replaced by C13.
Ans. 1537 cm-1

3- Using the mass value of N (nitrogen) as 14 / 6.02 x 1023,

calculate the vibration frequency (cm-1) for a N≡N bond?
Knowing that k : force constant for triple bond equals 15 x
105 dyne/cm.
Ans. 1905 cm-1
 The four primary regions of the IR spectrum

Bonds to H Triple bonds Double bonds Single Bonds

Group
frequency
Region Fingerprint
Region

O-H C≡C C=O C-C

N-H C≡N C=N C-N
C-H C=C C-O

4000 cm-1 2700 cm-1 2000 cm-1 1300 cm-1 400 cm-1

• Remember: light atoms and stronger bonds will vibrate at a high stretching
frequency (wavenumber).
▪ In “group frequency region” 4000-1300 cm-1:
• These types of infrared bands are called group frequencies because
they tell us about the presence or absence of specific functional
groups in a sample.

For example:
o C-H stretching vibrations usually appear between 3200 and 2800 cm-1
o Carbonyl (C=O) stretching vibrations usually appear between 1800
and 1600 cm-1

• This makes these bands diagnostic markers for the presence of a

functional group in a sample.

Define the group frequency region?

 ▪ The “Fingerprint” region 1300 to 400 cm-1:

• Many different vibrations, including C-O, C-C and C-N single

bond stretches, C-H bending vibrations, and some bands due
to benzene rings are found in this region.

• The fingerprint region is often the most complex and

confusing region to interpret, and is usually the last section of
a spectrum to be interpreted. However, the utility of the
fingerprint region is that the many bands there provide a
fingerprint for a molecule.

What is the importance of the fingerprint region?

▪ The “Fingerprint” region 1300 to 400 cm-1:
Small differences in structure of the molecule result in characteristic peaks in
this region
Different Molecular vibrations:
Methane CH4
 Selection rule (IR spectroscopy):
A molecule will absorb infrared radiation if the change in
vibrational states is associated with a change in the dipole
moment () of the molecule.

IR-Active (ex. H-Cl, H2O)

A condition for IR absorption spectroscopy is a net change in dipole

moment in a molecule as it vibrates.

 = Charge x distance

G.R: mono-atoms (ex. Ar) and homo-

nuclear diatomic molecules (ex. H2) are
IR inactive species (transparent to IR)
 How many vibrations (IR peaks) are possible (expected)
for a molecule?
Each atom has three degrees of freedom (corresponding to the Cartesian
coordinates), thus in an N-atom molecule there will be 3N degree of freedom.

Translation:
3 degrees of translational freedom.

Rotational transitions:
3 rotational freedom (nonlinear),
2 rotational freedom (linear).

Vibrations:
3N – 6 (nonlinear),
3N - 5 (linear).
 Calculate the vibrational degree of freedom of:
HCl, CO2, CH4 and H2O
Ans.
HCl: 3N – 5 = 6-5 = 1
CO2 : 3N – 5 = 9 – 5 = 4
CH4 : 3N – 6 = 15 – 6 = 9
H2O: 3N – 6 = 9 – 6 = 3
G.R:
IR peaks are sometimes less than the number of vibrational degrees of freedom.
The theoretical number of fundamental vibrations (3N-6 or 3N-5) will rarely be
observed.

1- overlap between peaks due to degeneracy.

2- low intensity of some peaks
3- symmetry of the molecule which cause lack of change in molecular dipole
4- frequencies could fall outside the measured spectral region (400-4000 cm –1 )
 calculate the possible
number of vibrational
bands for CO2

3N – 5 = 4 (theoretically)

Actually only 2 bands appear

Stretching higher energy than bending

 Infrared Instrumentation
Sample
IR Source compartment Detector
 Sample Cell:
The cell should be
transparent –inert- over the region of IR measurements.

- Alkali halides are widely used such as, KBr, and NaCl. Also
CaF2 is used. They are transparent for frequencies > 625 cm-1
- For frequencies < 600 cm-1, polyethylene cells are used.
- AgCl cells are used for moist samples but it easily gets
deformed and darkens on exposure to visible light

What is the type of sample cells used

for measuring IR for samples with
absorption peaks within the range
400-550 cm-1? Why?
Sample Preparation for IR
spectroscopy
Solid sample:
▪ 1- KBr Pellet technique:

A milligram of fine sample is mixed with about 100 mg of

dry KBr powder in a mortar
The mixture is then compressed to form a disc.
 Solid sample:

▪ 2- Nujol-Mull technique:

- Few milligrams of the powdered sample is grind in

a mortar.
- Few drops of mineral oil is added to form smooth
paste.
- The mineral oil used in this technique is called
Nujol which is heavy paraffin oil (chemically inert).
 Liquid sample: Why?
•Film of pure or solution in transparent solvent – 1- Water attacks the
not water- is “sandwiched” between two NaCl windows and the plates
plates) 2- water absorbs IR
causes interfering
• The pathlength (0.015 to 1 mm) can be adjusted
bands
by Teflon spacer

• Solvents used for IR spectroscopy:

Chloroform, carbon tetrachloride, carbon disulfides and cyclohexane
 Gaseous sample:

• A sample cell consists of a cylinder of

glass or sometimes a metal. The cell is
closed at both ends with an
appropriate window materials
(NaCl/KBr) and equipped with valves.

• The long path length (5 – 10 cm) is

needed

When the concentration of gas is low, to

increase the absorbance the path length is
increased to 10 m but …
• These gas cells do not offer a 10 m light
path in a straight line. Rather, this long
path is achieved by repeated
reflections (multipass cell) using a
group of mirrors
Some Applications
of
IR Spectroscopy
 Qualitative analysis
(Identification of substances)
• The probability that any two different compounds produce
identical IR spectra is almost zero.
The positions and magnitudes of peaks in the spectrum are
compared with stored IR profiles of pure compounds (Catalogs of
IR spectra are available for large number of compounds).
So if two compounds have identical IR spectra then both of them
must be samples of the same substances.

• IR spectra of two enantiomeric compounds are identical.

So IR spectroscopy fails to distinguish between enantiomers.
 Detection of impurities:

• IR spectrum of the test sample is compared with

the standard compound, spectrum of pure
reference. If any additional peaks are observed in
the IR spectrum, then it is due to impurities
present in the compound.

Example:
Ketone impurity in alcohols
 Quantitative analysis:
• The quantity of the substance can
be determined either in pure
form or as a mixture of two or
more compounds. In this,
characteristic peak corresponding
to the drug substance is chosen
and log I0/It of peaks for standard
and test sample is compared. This
is called base line technique to
determine the quantity of the
substance. Limited use
Example: In testing the alcohol content for drivers by measuring of BAC (Breath
Alcohol Content) using a “breathalyzer”-IR instrument.
 Presence of water in samples:
• If lattice water is
present, spectra will
contain 3 characteristic
bands at
3750, 3650 cm-1
and 1596 cm-1
• IR spectroscopy is also used in the identification of the different
components of paints. Structure of Paint and Varnish Chips Pieces of car
varnish are valuable trace evidence in case of hit and run accidents. By
determination of the used materials it is possible to identify the car model
involved in the accident.

• IR spectroscopy in Forensic Science, Hair Fiber Analysis. IR spectroscopy

is becoming a necessary tool in most forensic laboratories because of its
nondestructive nature and its ability to analyze with only a small amount of
sample (as low as a picogram or less) which makes it ideal for the limited-
quantity sample evidence usually associated with forensic investigations. If
chemical information from the hair can also be included, the ability to match
an unknown hair with a known source greatly increases.
 Near-IR spectroscopy (NIR) for nondestructive testing

• Which is more useful in Quantitative Analysis

mid-IR spectroscopy or NIR?
NIR absorption spectra are more useful for quantitative analysis
of compounds containing functional groups made up of hydrogen
bonded to carbon (C-H), nitrogen (N-H), and oxygen (O-H).
Such compounds can often be determined with accuracies and
precisions equivalent to ultraviolet-visible spectroscopy
 Some applications of NIR Absorption Spectrometry also include:

• In clinical chemistry, NIR is effective in analysis of native serum samples, e.g.

Triglycerides, cholesterol, urea and lactate concentrations.

• In petrochemistry, NIR has proven huge economical savings, since crucial

properties such as water content, density, viscosity, additive content, and hydroxyl
number can be measured in less than one minute. Gasoline parameters measured
with NIR cover octane number.

• Foods are complex mixtures, with the main components being water, proteins, fats
and carbohydrates. NIR spectroscopy is widely used in the food industry for the
quantitative analysis. NIR spectroscopy has been used, in the dairy industry to
examine milk. Milk consists of more than 80% water.
 Raman spectroscopy:
- It is used for the determination of IR vibrational spectra,
- Inactive IR vibrations can be detected as molecules do not required to
undergo change in the dipole moment

- Both IR and Raman involve change in the vibrational energy levels it is

complementary to IR.

G.R: Raman
spectroscopy is
complementary to IR

- This technique depends on scattering of light not the absorption

 Classical interactions of light and matter:

Raman spectroscopy:
-studies the frequency changes of light due to the interaction
with matter (inelastic scattering).
-Photons are not absorbed.
-Raman signal is 10-6 times weaker than the incident light
 Scattering

Rayleigh Raman ❑ Inelastic

scattering
❑ Elastic scattering ❑ The wavelength of ❑ The wavelength of
❑ The wavelength of the the scattered light the scattered light
scattered light is equal to is longer (smaller is shorter (larger
the wavelength of the E) than that of the E) than that of the
incident light incident light incident light
Stokes lines ❑ Anti-stokes lines
❑ It has high intensity ❑ low intensity lines ❑ low intensity lines
 Scattering

Raman
Rayleigh
ῡRayleigh = ῡSource of radiation
❑ Stokes lines ❑ Anti-Stokes lines
v= ho More frequent Less frequent

v= h(o - s) v= h(s - o)

ῡvib = ῡRayleigh - ῡStock ῡvib = ῡantistock - ῡRayleigh

ῡvib = ῡ o - ῡS ῡvib = ῡ antiS - ῡo

Example on Raman spectra:
 Problems on Raman spectroscopy:

1- The following data represent IR and Raman spectra of a given

substance. For these data calculate the wavenumber of IR vibrations
(active and inactive)
IR : 1670 cm-1 and 1100 cm-1
Raman : Rayleigh 3000 Å
Stokes 3060 Å, 3102 Å, 3158 Å
2- Raman spectra of certain substance gives the following stokes lines
using the source of radiation of 3800 Å. Calculate the corresponding
vibrational constant for the substance in cm-1.
Stokes lines: 3880 Å, 3950 Å, 4200 Å.

3- Using a source of radiation 3003 Å, Raman spectra of gaseous 1HCl at

strong stock peak 3283 Å is observed. Calculate the corresponding peak
for gaseous 2HCl where H is replaced by D (the observed peak in both
cases is due to stretching vibration in HCl) (Cl = 35.45, H = 1.009 and D =
2.004)
 Advantages of Raman over IR:

1- water can be used as a solvent

2- molecules do not required to undergo change in the dipole moment
3- symmetric vibrations are observable
4- incident light could be IR , UV or visible monochromatic light
5- quartz and glass cell can be used.
6- Single beam spectrophotometer is used as it measure scattered radiation
unlike IR technique (Double beams instrument should be used as we measure
absorption)

Schematic diagram for Raman spectrophotometer