Title

: Infrared Determination of a Mixture of Xylene Isomers

(Experiment 2 )
Objective : Determination of a Mixture of Xylene Isomers
Introduction

Quantitative infrared analysis is based on Beer's law, but a number of

problems can preclude its direct application. The use of an internal standard
provides a convenient means of overcoming all of the difficulties. In this
experiment the composition of a mixture of m-xylene and p-xylene is
determined using o-xylene as the standard. The bands used for the analysis
are:
m-xylene
o-xylene
p-xylene

880 cm-1
739 cm-1
795 cm-1

The spectrometer is usually set to read percent transmittance. The

reading can be treated by drawing a baseline tangent to both shoulders of
the band of interest and then determining Po and P as indicated in the
diagram below. Note that the position of zero transmittance must be
established accurately for this procedure to work satisfactorily.
100

%T
Po

Figure 2

Wavelength

The baseline method for quantitative determination in the

infrared region of the spectrum

The absorbance is calculated for each band and the ratio of the
absorbance of the desired constituent to that of the internal standard is

plotted versus the percent composition of the solution with respect to the
constituent.

Procedure :
1. A series of standard solutions in 10-mL volumetric flask are prepared
,based on following volume of isomers as depicted in table below
Xylene
isomer

Volume of isomer, mL
I

II

III

IV

Ortho-

0.2

0.2

0.2

0.2

Meta-

0.1

0.2

0.3

0.5

Para-

0.5

0.3

0.2

0.1

2. Cyclohexane were added to the mark , To each of the volumetric

flask .
3. spectra on each of the following solution are run from 2000 to 650 cm 1
.
a.*

Solution of 50% (vol/vol) o-xylene in cyclohexane.

b.*

Solution of 50% (vol/vol) m-xylene in cyclohexane.

c.*

Solution of 50% (vol/vol) p-xylene in cyclohexane.

d.

Standard solutions I-IV.

e.

Pure cyclohexane solvent.

f.

Unknown solution.

*These solutions have been prepared by lab assistant.

Results
i.

and Calculation

Table of absorbance peaks of infrared for xylene isomers

Peak, cm-1

Xylene isomers

ii.

o-xilen

741.75

m-xilen

861.17

p-xilen

792.25

Table of absorbanece, log

a.

Po
P

for xylene isomers

O-xilen isomer
Solution

% o-xilen

Po

log Po/P

0.2
x 100=2
10

99.50

96.25

0.014

II

0.2
x 100=2
10

99.625

95.875

0.017

III

0.2
x 100=2
10

98.60

96.70

0.008

IV

0.2
x 100=2
10

100.20

98.53

0.007

Unknown 1

82.55

78.47

0.022

Unknown2

84.00

82.50

0.008

Method of least square

Solutio

xi

xi yi

2
2
2
2

)
0.014
0.017
0.008
0.007

4
4
4
4

0.028
0.034
0.016
0.014

x i=8

y i=0 .046

x i2=16

x i yi =0 . 092

x i( 0xylene)

n
I
II
III
IV

n=4

y i (log P /p
o

m=

n=4 , x=

x=

xi
n

8
4
x =2

yi
n=4 , x=
n
y=

m=

( 82 )(0 .0460 . 0115)

( 82 )2
m=0.006

0.046
4
y=0.0115

( x i x )( y i y )
2
( x i x )

b= ymx

b=0.01150 .006 ( 2 )
b=-0.0005

b.

M-xilen isomer
Solution

% m-xilen

Po

log Po/P

0.1
x 100=1
10

97.00

95.125

0.008

II

0.2
x 100=2
10

98.875

94.63

0.019

III

0.3
x 100=3
10

99.00

97.20

0.008

IV

0.5
x 100=5
10

98.55

97.20

0.006

Unknown1

89.0

86.5

0.01

Unknown 2

89.0

84.95

0.02

Method of least square

Solution

x i( M xylene)

I
II
III
IV

1
2
3
5
x i=
11

y i (log
Po/p )
0.008
0.019
0.008
0.006
y i= 0.04

x i yi

x i2

1
4
9
25
2
x i =
39

0.008
0.038
0.024
0.030
x i y i=
0.10

n=4
n=4 , x=

x=

xi
n

11
4
x =2.75

n=4 , x=

m=

m=

( x i x )( y i y )
2
( x i x )
( 112 .75 ) (0 . 040 . 01)
( 112.75 )2
m=0.004

yi
n
b= ymx

y=

0.04
4
y=0.01

b=0.010 .004 ( 2.75 )

b=-0.001

c.

P-xilen isomer

Solutio

% p-xilen

Po

log Po/P

0.5
x 100=5
10

96.875

95.37

0.007

II

0.3
x 100=3
10

98.375

95.75

0.012

III

0.2
x 100=2
10

98.80

97.90

0.004

IV

0.1
x 100=1
10

99.80

98.00

0.008

Unknow

86.5

82.95

0.018

85.0

82.11

0.015

n1
Unknow
n2

Method of least square

Solution

x i( pxylene)

I
II
III
IV

5
3
2
1
x i=
11

xi

y i (log
Po/p )
0.007
0.012
0.004
0.008
y i= 0. 03

25
9
4
1
2
x i =
39

xi yi

0.035
0.036
0.008
0.008
x i y i=
0.08
7

n=4

y=

n=4 , x=

x=

xi

0.03
4
y=0.008

11
4
x =2.75
m=

n=4 , x=

yi

( x i x )( y i y )
2
( x i x )

n
m=

( 112.75 ) (0 .030 . 008)

( 112.75 )2
m=0.003

b=0.0080.003 ( 2.75 )
b= ymx

b=-0.0003

Conclusion :
Percentage of
o-xylene
m-xylene
p-xylene

Unknown 1
2.6 %
1.25 %
4.5 %

Unknown 2
1%
2.55 %
3.75 %

Questions
1.

What is the criterion for absorption to occur in the infrared region?

In order to absorb infrared radiation, a molecule must undergo a net
charge in dipole moment as a consequence of its vibrational or
rotational motion.
For a molecule to absorb IR, the vibrations or rotations within a
molecule must cause a net change in the dipole moment of the
molecule. The alternating electrical field of the radiation interacts with
fluctuations in the dipole moment of the molecule. If the frequency of
the radiation matches the vibrational frequency of the molecule then
radiation will be absorbed, causing a change in the amplitude of
molecular vibration.
For example, the charge distribution around a molecule such as HCl is
not symmetric because the Cl has a higher electron density than H.
So, HCl has significant dipole moment and is said to be polar. The
dipole moment is determined by the magnitude of the charge
difference and the distance between the two center of charge. No net
charge in dipole moment occurs during the vibration or rotation of
homonuclear species such as O2, N2 or Cl2. So, they cannot absorb
the IR radiation. The absorption of IR radiation follows the Beers Law.
So, the absorption is directly related to the concentration of specific
bonds (or functional groups) within a sample and the concentration of
specific analytes.

2.

What types of molecular vibration are associated with infrared

absorption?

In Molecular vibrations the positions of atoms in a molecules are not

fixed; they are subject to a number of different vibrations. Vibrations
fall into the two main categories of stretching and bending. Stretching
is a change in inter-atomic distance along bond axis. While bending is
change in angle between two bonds. There are four types of bend
which is Rocking , Scissoring ,Wagging and Twisting.
3.

Define the following terms:

a. Chromophore
A chromophore is the part of a molecule responsible for its color.
[1]
The color that is seen by our eyes is the one not absorbed within
a certain wavelength spectrum of visible light. The chromophore is a
region in the molecule where the energy difference between two
separate molecular orbitals falls within the range of the visible
spectrum. Visible light that hits the chromophore can thus be
absorbed by exciting an electron from its ground state into
an excited state.

b. Auxochrome
An auxochrome is
a
group
of
atoms
attached
to
a chromophore which modifies the ability of that chromophore
to absorb light. They themselves fail to produce the colour; but
when present along with the chromophores in an organic compound
intensifies the colour of the chromogen .Examples include
the hydroxyl
group (-OH),
the amino
group (-NH2),
the aldehyde group (-CHO), and the methyl mercaptan group (SMe).
An auxochrome is a functional group of atoms with nonbonded
electrons when attached to a chromophore, alters both
the wavelength and intensity of absorption. If these groups are in
direct conjugation with the pi-system of the chromophore, they may
increase the wavelength at which the light is absorbed and as a
result intensify the absorption. A feature of these auxochromes is
the presence of at least one lone pair of electrons which can be
viewed as extending the conjugated system by resonance.

c. Bathocrhomic shift

Bathochromic shif is a change of spectral band position in

the absorption, reflectance, transmittance, or emission spectrum of
a molecule to a longer wavelength (lower frequency). Because
the red color in the visible spectrum has a longer wavelength than
most other colors, this effect is also commonly called a red shift.

This can occur because of a change in environmental conditions: for

example, a change in solvent polarity will result in solvatochromism.

d. Hypsochromic shift
Hypsochromic shift is a change of spectral band position in
the absorption, reflectance, transmittance, or emission spectrum of
a molecule to a shorter wavelength (higher frequency). Because
the blue color in the visible spectrum has a shorter wavelength than
most other colors, this effect is also commonly called a blue shift.
This can occur because of a change in environmental conditions: for
example, a change in solvent polarity will result in solvatochromism.

e. Hyperchromism
Hyperchromism is increasing of absorption of electomagenetic
radiation that exhibited by an ordered structure above the predicted
on the basis of its constituent .
f. Hypochromism
Hyperchromism is decreasing of absorption of electomagenetic
radiation that exhibited by an ordered structure above the predicted
on the basis of its constituent .
4. Sulfur dioxide is a nonlinear molecule. How many vibrational
modes will this compound have? How many absorption peaks
would sulfur dioxide be expected to have?
Sulphur dioxide , contain 3 atom which is 2 oxygen atoms and one sulphur
atom.
3 n6

3
T h e vibrationmodes is 3

5. What are the advantages of a Fourier transform

spectrometer compared with a dispersive instrument?

infrared

FT-IR Advantages
The modern FT-IR spectrometer has three major advantages over a
typical dispersive infrared spectrometer. These advantages are the
reason FT-IR is now the standard tool, having largely displaced dispersive
instruments by the mid-1980s.
Multiplex Advantage
Each point in the interferogram contains information from each
wavelength of light being measured. Every stroke of the moving mirror
equals one scan of the entire infrared spectrum, and individual scans can
be combined to allow signal averaging. In the dispersive instrument,
every wavelength across the spectrum must be measured individually as
the grating scans. This can be a slow process, and typically only one
spectral scan of the sample is made in a dispersive instrument. The
multiplex advantage means many scans can be completed and averaged
on an FT-IR in a shorter time than one scan on most dispersive
instruments.

Precision Advantage
An FT-IR spectrometer uses a laser to control the velocity of the moving
mirror and to time the collection of data points throughout the mirror
stroke. This laser is also used as a reference signal within the instrument.
The interferogram of the laser is a constant sine-wave, which provides the
reference for both precision and accuracy of the infrared spectrometer.
Well-designed FT-IR spectrometers rely exclusively on this reference laser,
rather than any external reference sample. In this case, spectra collected
with an FT-IR spectrometer can be compared with confidence whether
they were collected five minutes or five years apart. This capability is not
available on a dispersive infrared system, or any system requiring
external calibration standards