Olsen A.

Vertudazo
BS Chemistry – 3
Chem 146 – Analytical chemistry II

Problem Set No. 5

Infrared Spectroscopy
1. Indicate whether the following motions will be active or inactive in the IR region.
a. C-C stretch in ethane = active
b. C – C stretch in CH3-CH3 = active
c. Rotation of N2 = inactive
d. C = C stretch in ClHC = CHCl = inactive
e. bending vibrations in H2S = active

2. The infrared spectrum of CO shows a vibrational absorption peak at 2100 cm-1. What is
the force constant of the CO bond?

GIVEN:
v̅ = 2100 cm-1

ASKED:
k=?

FORMULA:
1 k
v̅ = 2πc √μ (c is the speed of light (3 x 1010 cm))

k = (v̅ x 2𝜋c)2 𝜇 (EQUATION 1)

* Calculate the reduced mass (𝜇) :

m1 m2
𝜇=m (EQUATION 2) (m1 = mass of carbon; and m2 = mass of oxygen)
1 + m2
 g
Atomic mass of carbon = 12
mol

Convert the mass into kg:

12 g 1 kg kg
x 1000 g = 12 x 10-3 mol
mol

Calculate the m1:

12 x 10−3 kg 1 mol
m1 = x 6.0 x 1023 atom x 1 atom = 2.0 x 10-26 kg
1 mol

g
Atomic mass of oxygen = 16 mol

Convert the mass into kg:

16 g 1 kg kg
x = 16 x 10-3 mol
mol 1000 g

Calculate the m2:

16 x 10−3 kg 1 mol
m2 = x 6.0 x 1023 atom x 1 atom = 2.7 x 10-26 kg
1 mol

Substitute the vales of m1 and m2 in equation 2:

m1 m2 (2.0 x 10−26 kg)(2.7 x 10−26 kg)
𝜇=m = (2.0 x 10−26 kg+ 2.7 x 10−26 kg) = 1.1 x 10-26 kg
1 + m2

Substitute the value of 𝜇 in the equation 1:

k = (v̅ x 2𝜋c)2 𝜇
k = [(2100 cm-1)(2)(3.14)(3 x 1010 cm s-1)]2 (1.1 x 10-26 kg)
k = (1.56531 x 1029 s-2)(1.1 x 10-26 kg)
k = 1.72 x 103 s-2 kg
Convert s2- kg into N / m:
1 N m−2
(1.72 x 103 s-2 * kg) (1 kg m−1s−2)

k = 1.72 x 103 N / m

3. Discuss briefly the following:

a. classical and quantum mechanics of molecular vibrations
 - In classical (Newtonian) mechanics, it can calculate the
correct vibration frequencies. The basic assumption is that each vibration can
be treated as though it corresponds to a spring. In the harmonic
approximation, the spring obeys the Hooke’s Law. It is stated that the force
required to extend the spring is proportional to the extension. On the other
hand, in quantum mechanics, the harmonic approximation of the potential
energy is a quadratic function of the normal coordinates. Solving the
Schrodinger wave equation, the energy states for each normal coordinate are
given by:
1 1 1
En = h (n + 2 ) v = h (n + 2) 2𝜋
Where n is a quantum number that can be the values of 0,1,2,3..
In molecular spectroscopy, there are several types of molecular energy are
studied and several quantum numbers are used, this vibrational quantum
number is often representing as v. The difference in energy when n or v
changes by 1. Hence, it is equal to hv, the product of the Planck constant and
the vibrational frequency derived using classical mechanics.

b. dispersive and non-dispersive IR instruments

- Dispersive infrared spectrometers generate spectra by
optically dispersing the incoming radiation into its frequency or spectral
components. Dispersive IR spectrometers use a diffraction grafting in a
monochromator to disperse the different wavelengths of light. On the other
hand, non-dispersive infrared (NDIR) spectroscopy usually used to measure
a single constituent of an air sample. The word non – dispersive implies that
the instrument like NDIR spectroscopy does not use a monochromator.

4. A crystalline material is believed to be either a substituted hydroxylethyl cyanamide (l) or

an imino oxazoline (II)
(+) O O
N ≡ C – NH2 – CH – CH2OH HN = CH – NH – C – CH2
(l) (II)

Sharp bands are located at 3330 cm-1 and 1600 cm-1 but there are no bands at 2300
cm-1 or 3600 cm-1. Which structure fits the infrared data. Explain your answer.
- Structure 2 fits the IR data because 2300 cm-1 and 3600 cm-1 represents as a
nitrile and alcohol respectively. Since there is cyanide and alcohol in the first
structure, Thus, structure 2 fits the IR data.
5. Suggest a possible structure for the compound with the following attached spectra

ANSWER:
E. Cyclopentanol

ANSWER:
C. dipropyl ether

6. Under what conditions will you observe IR absorption?

- There are three conditions that analyze or observe IR absorption: it can experience
a change in dipole moment, whether it is induced or permanent, it should have resonant
frequencies that are in the infrared frequency range of 100 – 400 cm-1, and ideally, it should
be not overly soluble in a nonpolar solvent, which is ideal since many analyses are carried out
using a solvent like CS2 or CCl4.
7. How many vibrational modes are observed for CO2? Which mode is IR active? Where is
it observed in the IR spectrum?
- Since CO2 is a triatomic linear molecule, the degrees of vibrational modes for linear
molecules can be calculated using the formula below:
3N – 5
3(3) – 5 = 4
Thus, CO2 has 4 vibrational modes. There are 4 vibrational modes of CO2: V1
(symmetric C – O stretch); V2 (bend); and V3 (asymmetric C – O stretch). The modes that
are IR active in CO2 are: asymmetric stretch; and bend because asymmetric stretch does
result in a change in dipole moment, so it is IR- active; and bend also results in a change in
dipole moment so it is also IR- active. Since there 4 vibrations but there only 3 vibrations
that are mentioned because the bend can occur in the y – direction and the z – direction but
these two motions are the same. Just deforming in different directions, the bend is said to be
degenerate and it considered or accounting for the fourth vibration. In over all, CO2 has 2
IR- active vibrations. The CO2 asymmetric stretch observed at 2345 cm-1 and two CO2 bends
predicted at 667 cm-1.

8. How does the Michelson interferometer work?

- The Michelson interferometer produces interference fringes by splitting a beam of
light so that one beam strikes a fixed mirror and the other a movable mirror. When the
reflected beams are brought back together, an interference pattern result.

9. Discuss the principle and applications of the following sampling techniques.

a. Attenuated Total Reflectance (ATR)
- It is a sampling technique that used in conjunction with IR spectroscopy
which enables samples to be examined directly in the solid or liquid state
without further preparation. IR spectroscopy by ATR is applicable to the
same chemical and biological systems as the transmission method. ATR-
IR has been applied to microfluidic flows of aqueous solutions by
engineering microreactors with built – in apertures for the ATR crystal,
allowing the flow within the microchannels to pass across the crystal
surface for characterization, or in dedicated flow cells.

b. Diffuse Reflectance (DR)

- In diffuse reflectance spectroscopy, the electromagnetic radiation
reflected by roughened surfaces is collected and analyzed. This technique
is also applied in FTIR region, it is termed as diffuse reflectance infrared
Fourier transform spectroscopy (DRIFTS). The light incident onto a solid
sample may be partly reflected regularly (specular reflection) by the
sample surface, partly scattered diffusely, and partly penetrates into the
sample. DRS associated with the reflected lights which are produced by
diffuse scattering. Since the regular reflection distorts the DRS spectra,
 hence, the regular reflection component should be eliminated in diffuse
reflectance measurement. This technique is used for powders and solid
samples having rough surface such as paper cloth. In this technique, the
particle size, homogeneity, and packing density of powdered samples play
important role on the quality of spectrum. A sample with small particle
size having narrow size distribution is preferred. Hence, in order to obtain
a qualified spectrum, the sample should be ground into smaller size.

c. Specular Reflectance (SR)

- It is a technique that basically involve a mirror – like reflection from the
sample surface that occurs when the reflection angle equals the angle of
incident radiation. The most common applications of this technique are
evaluation of surfaces such as: coating, thin films, contaminated metal
surface.

d. Mulling Technique
- In this technique, the finely crushed sample is mixed with Nujol (mulling
agent) in a marble or agate mortar, with a pestle to make a thick paste. A
thin film is applied onto the salt plates. This is then mounted in a path of
IR beam and the spectrum is recorded.

10. What are the requirements of a good quality IR spectra?

- There are five requirements of a good spectrum: low noise, little or no baseline offset,
a flat baseline, peaks on scale, and a lack of spectral artifacts.

11. Submit a representative of IR spectra that shows the distinguishing IR bands indicative of
the following: alkanes, alkenes, alkynes, aromatics, alcohols, ketones, aldehydes, esters,
carboxylic acids, amines, amides, anhydrides.
1. ALKANE 2. ALKENE

C = C (1600 - 1680 cm-1 )

Medium bands

C – H bend (1375 - 1450 cm-1 )

Medium bands

C – H stretch (2850 - 3000 cm-1 )

Strong bands

3. ALKYNE 4. ALCOHOL

C ≡ C (2250 – 2100 cm-1 )

Weak bands

O – H (3700 – 3000 cm-1 )

Strong bands
5. KETONE 6. ALDEHYDE

C = O (3700 – 3000 cm-1 )

Strong bands

C = O (3700 – 3000 cm -1
)
Strong bands C - H (2800 cm-1 )
Weak bands

7. AROMATIC 8. ESTER

C = O (1750 – 1730 cm-1)

Strong bands

C = C (1600 cm-1 ) C - O (1200 cm-1)

Strong bands
Medium - Weak bands
9. CARBOXYLIC ACID 10. AMINES

N – H bend (1600 cm-1)

Medium - Strong bands

C - N (1100 cm-1)
Medium - Strong bands
C = O (1700 cm-1)
Strong bands
C - O (1300 cm-1)
Strong bands
11. AMIDE 12. ANHYDRIDE

C = O (1760 cm-1)
Strong bands

C = O (1670 – 1640 cm-1)

C - O (1300 - 1000 cm-1)
Strong bands Strong bands
N – H stretch (3300 cm-1)
Medium bands