IR Spectrum

Potassium
ferricyanide
obtained from FT-IR
- TANYA SHARMA
(Inorganic Group-3)
 01 02
Theory Sample
Preparation

03
Hands-on operation to
obtain IR spectrum and
spectrum analysis
01
THEORY
▪ Potassium ferricyanide

▪ Infrared Spectroscopy

▪ FT-IR Spectroscopy
Potassium ferricyanide

Potassium ferricyanide is a
chemical compound with a
chemical formula K3[Fe(CN)6].

It is manufactured by
passing chlorine through a
solution of potassium
ferrocyanide. Potassium
ferricyanide thus separates
from the solution.
 Infrared Spectroscopy
Infrared Spectroscopy is an important branch of spectroscopy
which can identify particular functional groups present in a
molecule.
It works on the principle that the molecules vibrate at specific
frequencies and these frequencies fall in IR portion of
electromagnetic spectrum.
When IR radiation is incident on a sample, it absorbs radiations
at frequencies similar to its molecular vibration frequencies and
transmit other frequencies. Frequencies of absorbed radiation are
detected by infrared spectrometer, and a plot of absorbed energy
against frequency called as ‘infrared spectrum’, can be obtained.
Only those molecular vibrations appear in the IR spectrum which
are IR active (or absorb IR light).
 FT-IR Spectroscopy
FTIR stands for Fourier Transform Infrared, the preferred
method for infrared spectroscopy.

FTIR is a technique that uses infrared light to observe

properties of a solid, liquid or gas. It works on the
principle of vibrational spectroscopy.

It is used in many different applications to measure the

absorption, emission and photo-conductivity of matter by
shining a narrow beam of infrared light at the matter in
various wavelengths and detecting how the matter
responds to each wavelength. Once the data has been
obtained, it is converted into digital information using a
mathematical algorithm known as the ‘Fourier Transform’.
Diagrammatic representation of FT-IR
Michelson Interferometer
02
SAMPLE
PREPARATION
 Sample Preparation

For recording IR Spectra, the sample should be properly dried as

water absorb near 3710 and 1630 cm-1.The sample should be
perfectly dried, since cell materials (NaCl, KBr) are usually spoiled
by the moisture. There are several methods by which a solid sample
can be prepared.

(a) As a pressed disc: It involves the mixing of sample with powdered

KBr. A translucent pellet of this powder mixture is formed by
pressing it in a mechanical pressure. The main advantage of using
KBr is that it does not interfere with the bands due to compound
since KBr is transparent to IR and thus give better spectra.
 Sample Preparation

(b) As a mull or paste: Finely ground compound is mixed with an oily mulling
agent (usually Nujol) using a pestle and mortar. A thin film of the mull is
placed between two flat plates of NaCl and the spectrum is measured. The
main disadvantage of this method is that nujol has absorption bands at 2924-
2860, 1462, 1380 cm-1, therefore no information about the observed
compound can be obtained in this region.
(c) As a film: The third method is to dissolve the solid sample in a non-
hygroscopic solvent usually methylene chloride or carbon tetrachloride. A drop
of this solution is deposited on surface of KBr or NaCl plate. The solution is
then evaporated to dryness and the film thus formed on the KBr disc is
analysed directly to obtain the IR spectrum.
03
HANDS- ON OPERATION
TO OBTAIN IR SPECTRUM
AND ITS ANALYSIS
 Hands- on operation to obtain IR spectrum
of Potassium ferricyanide

❑ First step is sample preparation which has already been discussed.

❑ The second step is to obtain an interferogram of the background which consists of
the IR- active atmospheric gases carbon dioxide and water vapours. This
interferogram gives the spectrum of background.
❑ In the third step, spectrum of the sample under investigation is obtained by the
same procedure. This spectrum contains absorption bands from the sample as well
as the background.
❑ The ratio between the single beam sample spectrum and the single beam
background spectrum gives the spectrum of the sample. Computer software
automatically subtracts the spectrum of the background from the sample spectrum.
❑ Finally the data obtained is analysed by assigning the observed absorption
frequency bands in the sample spectrum to appropriate normal modes of vibrations
in the molecules.
Absorbance Infrared(IR) Spectra

The thermal
coefficient of
potential
should be
small.
Infrared Spectra

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 Peak Identification
FTIR of K3 [Fe(CN)6 ] as shown in figure
exhibit peaks at (3464 cm-1, 1630 cm-1 ),
(2118, 2076, 2043) cm-1 and 511 cm-1
which are attributed to ν (OH) of lattice
water (symmetric and antisymmetric)
(H-O-H), ν(C≡N) and ν (Fe-CN) vibrational
% Transmittance

modes respectively.
 Analysis of
IR spectrum of Potassium ferricyanide

The IR spectrum is divided into three wavenumber regions: far-IR spectrum (<400 cm-1), mid-
IR spectrum (400-4000 cm-1), and near-IR spectrum (4000-13000 cm-1). The mid-IR spectrum
is the most widely used in the sample analysis, but far- and near-IR spectrum also contribute
in providing information about the samples analyzed.
The mid-IR spectrum is divided into four regions:
•the single bond region (2500-4000 cm-1),
•the triple bond region (2000-2500 cm-1),
•the double bond region (1500-2000 cm- 1), and
•the fingerprint region 600-1500 cm- 1
 Steps to interpret FT-IR
•Step 1: Identification of number of absorption bands in the entire IR spectrum. If the sample
has a simple spectrum (has less than 5 absorption bands, the compounds analyzed are simple
organic compounds, small mass molecular weight, or inorganic compounds (such as simple
salts). But, if the FTIR spectrum has more than 5 absorption bands, the sample can be a
complex molecule.

•Step 2: Identifying single bond area (2500- 4000 cm-1). There are several peaks in this area:
A broad absorption band in the range of between 3650 and 3250 cm-1, indicating hydrogen
bond. This band confirms the existence of hydrate (H2O), hydroxyl (- OH), ammonium, or
amino. For hydroxyl compound, it should be followed by the presence of spectra at
frequencies of 1600–1300, 1200–1000 and 800–600 cm-1. However, if there is a sharp
intensity absorption in the absorption areas of 3670 and 3550 cm-1, it allows the compound to
contain an oxygen- related group, such as alcohol or phenol (illustrates the absence of
hydrogen bonding).
 Steps to interpret FT-IR
•Step 3: Identifying the triple bond region (2000-2500 cm-1)
For example, if there is a peak at 2200 cm-1, it should be absorption band of C≡C. The peak is
usually followed by the presence of additional spectra at frequencies of 1600– 1300, 1200–
1000 and 800–600 cm-1.

•Step 4: Identifying the double bond region (1500-2000 cm-1)

Double bond can be as carbonyl (C = C), imino (C = N), and azo (N = N) groups.

•Step 5: Identifying the fingerprint region (600-1500 cm-1)

This area is typically specific and unique. This region show absorption band of C-F, C-I,C-Br
also.
RESULT
The IR Spectrum of Potassium
ferricyanide obtained from FT-IR
is successfully analysed.
 REFERENCES
❑ Nakagawa I, Shimanouchi T. Infrared spectroscopic study on the co-
ordination bond-II: Infrared spectra of octahedral metal cyanide complexes.
Spectrochimica Acta. 1962;18(1):101-113
❑ http://dx.doi.org/10.1590/1980-5373-MR-2015-0786
❑ https://www.researchgate.net/figure/Absorbance-infrared-spectra-of-potassium-
ferricyanide-obtained-as-potassium-bromide_fig1_23436451
❑ https://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/S001174BS/P001858/
M030452/ET/1526641296P10_M26_ET.pdf
❑ https://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/S000831ME/P001676
/M030244/ET/1525950185Module-2_Unit5_COM-I.pdf
❑ VIBRATIONAL SPECTRA OF CRYSTALLINE POTASSIUM FERRIAND
FERROCYANIDE Yu. A. Klyuev Zhurnal Prtkladnoi Spektroskopii, Vol. 3,
No. 1, pp. 42-48, 1965
Thanks!
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