Course Title: Analytical Chemistry-II

Course Code: CHEM-3013

Assignment topic: FT-IR Spectroscopy, Fourier analysis, Interferometry,
noise and its control
Submitted to: Miss Nafeesa Sajjad
Submitted by: Samra
Roll no. 18104008-006
Date: 20/12/2020
 FT-IR Spectroscopy
Introduction:
FT-IR stands for Fourier Transform Infrared, the preferred method of Infrared spectroscopy,
which is used to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. It
is a technique based on determination of interaction between IR radiation and sample that can be
solid, liquid or gas. It measures the frequencies at which sample absorbs and also the intensities
of these absorptions. The term Fourier Transform Infrared spectroscopy originates from the fact
that a Fourier Transform (a mathematician process) is required to convert the raw data into actual
spectrum.

Principle:
 All infrared spectroscopies act on the principle that when infrared (IR) radiation passes through
a sample, some of the radiation is absorbed. The radiation that passes through the sample is
recorded. Because different molecules with their different structures produce different spectra,
the spectra can be used to identify and distinguish among molecules. In this way, the spectra are
like people’s fingerprints or DNA: virtually unique.

Instrumentation:
 Source:
 An optical system which uses interferometer,
a) Beam splitter
b) Moving mirror
c) Stationary mirror
 Sample
 Detector

Source:
Source can be Incandescent lamp, High pressure mercury arc, and Nernst Glower or a Globar
source.
Interferometer:
The heart of FT-IR is Michelson interferometer. The monochromator is replaced by
interferometer which divides the radiant beam, then recombines them with in order to produce
repetitive interference signals measured as a function of optical path difference as the name
implies interferometer produces interference signals which contain IR spectral information
generated after passing through sample.
It consist of three active components:
a) Beam splitter
b) Moving mirror
c) Stationary mirror
The position of movable mirror is controlled by He-Ne laser. Between these two mirrors beam
splitter at 45 degree from the position of movable mirror is set. A parallel beam of radiations
from IR source pass on the mirror through beam splitter. Beam splitter divides the beam and
transmit half of the incoming radiation to movable mirror and half to the fixed mirror. Upon
reflection from the fixed and movable mirror, the light is recombined at beam splitter.
Sample:
The beam enters the sample compartment.
Detector:
Photo conductive or pyroelectric conductors are used. The beam finally passes to detector for
final measurements. Then the measured signals are digitalized and sent to the computer where
Fourier transformation takes place.
How does FT-IR works?
Michelson interferometer:
FT-IR uses interferometry to record information about the material placed in IR beam. An FTIR
uses Michelson Interferometer which is typically based on Experimental Setup; an example is
shown in Figure below. The interferometer consists of a beam splitter, a fixed mirror, and a
mirror that translates back and forth, very precisely. The beam splitter is made of a special
material that transmits half of the radiation striking it and reflects the other half. Radiation from
the source strikes the beam splitter and separates into two beams. One beam is transmitted
through the beam splitter to the fixed mirror and the second is reflected off the beam splitter to
the moving mirror. The fixed and moving mirrors reflect the radiation back to the beam splitter.
Again, half of this reflected radiation is transmitted and half is reflected at the beam splitter,
resulting in one beam passing to the detector and the second back to the source.
Optical Path Difference (OPD) is the difference between the two beams travelling through the
two arms of an interferometer. OPD is equal to the product of the physical distance travelled by
the moving mirror (multiplied by 2, 4, or other multiplier, which is a function of the number of
reflecting elements used) and n, the index of refraction of the medium filling the interferometer
arms (air, Nitrogen for purged systems, etc.). The raw FT-IR data consists of pairs of values
(signal, OPD, etc.). FT-IR has a natural reference point when the moving and fixed mirrors are at
the same distance from the beam splitter. This condition is called the zero path difference or
ZPD. The moving mirror displacement, Δ, is measured from the ZPD. In Figure 2 the beam
reflected from the moving mirror travels 2Δ further than the beam reflected from the fixed
mirror. The relationship between the optical path difference and mirror displacement, Δ, is:
OPD = 2Δn

Applications of FTIR:
 Identification of organic and inorganic compound.
 Identification of components of unknown mixture.
 Analysis of solids, liquids and gases.
 Analysis of micro sample such as in forensic analysis.
 It is used as a detector in chromatography.
 Study of complex molecules
 Detection of impurities in compound

Advantages:
 Fast and accurate analysis
 Sensitive and easy
 We can determine even small quantity of analyte.
 Simpler mechanical design
 Relatively inexpensive

Fourier analysis:
Introduction and History:
In Fourier analysis a periodic wave form is defined in terms of trigonometric functions. It
identify patterns or cycles in a series of data set which has already been normalized.
The method gets its name from a French mathematician and physicist named Jean Baptiste
Joseph Baron de Fourier, who lived during the 18th and 19th centuries. Fourier analysis is used in
electronics, acoustics and communications.

Explanation:
Fourier analysis is a type of mathematical analysis that attempts to identify patterns or cycles in
a time series data set which has already been normalized. In particular, it seeks to simplify
complex or noisy data by decomposing it into a series of trigonometric or exponential functions,
such as sine waves. Each of these sine waves would have a specific cycle length, amplitude, and
phase relationship with the other sine waves, which then could be added back together to
reconstruct the observed data.By first identifying and removing any effects of spurious trends or
other complicating factors from the data set, the effects of periodic cycles or patterns can be
identified more accurately, leaving the analyst with a better estimate of the direction that the data
under analysis will take in the future. Fourier analysis may sound complex, but it actually makes
good sense. Essentially it theorizes that complicated time series  data can be construed as the sum
of simpler functions such as those described by trigonometry. Numerous studies have explored
Fourier analysis for practical value in forecasting stock market price. Because Fourier analysis
seeks to break down repetitive waveforms into harmonic components and the stock market
doesn't move in a well-defined and repetitive manner, results are mixed, as most similar
strategies are. Fourier analysis methods are frequently implemented in algorithmic trading  as
a technical analysis  tool for forecasting market direction and trends. Recent research that has
sought to vigorously examine the usefulness of Fourier analysis in predicting stock prices has,
however, shown the method to be a failure. Today, the subject of Fourier analysis encompasses a
vast spectrum of mathematics. In the sciences and engineering, the process of decomposing a
function into oscillatory components is often called Fourier analysis, while the operation of
rebuilding the function from these pieces is known as Fourier synthesis.

In the image, you can see the Fourier analysis of time signal of open string. A note of the bass
guitar.

Applications of Fourier analysis:

 Equalization of audio recordings
 Image Processing for removing periodic or anisotropic artefacts
 Cross-correlation of same types of images
 X-Ray Crystallography
 Passive Sonar which is used for classifying targets as per machinery noise
 Generation of sound spectrograms and so many other areas where people can benefit
from this amazing analysis method.
Interferometry:
Interferometry is techniques in which waves, usually electromagnetic waves, are superimposed,
causing the phenomenon of interference, which is used to extract information. In analytical
chemistry, interferometers are used to measure lengths and the shapes of optical components
with nanometer precision; these are the highest precision length measuring instrument in
existence.

Principle:
In interferometer electromagnetic waves are superimposed causing the phenomena of
interference, used to extract information. This works when two waves of same frequency
combine, the resulting wave pattern is determined by phase difference between two waves. Most
interferometers use light or other forms of electromagnetic wave.
Michelson configuration, a single incoming beam of coherent light will be split into two identical
beams by beam splitter. The difference in the distance travelled by each beam creates phase
difference between them. This could be a physical change in path length itself or a change in the
refractive index along the path.

Noise and its control:

Noise is the random fluctuations occurring in a signal that are inherent in the combination of
instruments and methods It is usually common to record several interferograms involving
repetitive scans of the moveable mirror and then adding them together. An advantage of using
multiple scans is that the signal of each scan is additive. Noise is a random process so adding
together several scans leads to a reduction due to cancelling out of some of the noise. Therefore,
adding together multiple scans will lead to an improvement in the signal-to-noise ratio. The
improvement in the signal-to-noise ratio actually goes up as the square root of the number of
scans. This means that recording twice as many scans, which takes twice as long, does not
double the signal-to-noise ratio. As such, there are diminishing returns to running excessively
large numbers of scans if the sample has an especially weak signal (e.g., due to a low
concentration) because the time for the experiment can become excessive

Noise Control:
Noise can also be controlled by following ways:
 Noise control by periodically measuring a standard and correcting for any change in
signal.
 Noise is minimized by chopping.
 Physical isolation of instruments.
 Noise can be significantly reduced by cooling the system.
 Johnson noise can be reduced by reducing the temperature of the device.
 Noise also controlled by absorption, damping, decoupling, mass and flow control.
References:
 Fundamentals of Analytical Chemistry F James Holler Stanley R. Crouch Pg. no.749-
750
 Instrumental analysis, Skoog, Holler Crouch. Pg. no. 488-493
 Introduction to instrumental analysis Robert D. Braun Pg. no. 372-373
 Analytical Chemistry by G.D Christian