Session 7 (IR)
Session 7 (IR)
Session 7 (IR)
Qualitative and
Quantitative Analysis using
IR Spectrometer
(Session 7)
Qualitative and Quantitative Analysis
Ultimate goal of IR analysis is identification of the substance
measured or determination of its quantity.
Remember!
Specific bonds present in a molecule give rise to absorption
bands at specific ’s in the IR region corresponding to the
types bonds.
Qualitative analysis based on the IR makes use of information
acquired from A measurement at specific ’s to each bond
type;
The information so obtained can provide the basis for
identifying and elucidating the structure of a sample
molecule.
Applications of IR Spectra: Qualitative
Analysis
The IR spectra are generally transmission spectra:
Calibrated mostly in wave numbers (cm-1 ) or in wave length (μm);
The baseline is at the top of the chart and marks 100% T;
Thus, IR peaks emerge from top and extend down to the 0% T
level indicating max absorption (see Fig. 26 & 27).
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Important Spectral Regions in IR
Most characteristic bands appear in the peak ID region,
which is from about 4000 cm-1 to 1500 cm-1
of cpds.
Bands in this region are due to single bonds which are nearly
of similar energies;
The absorption bands are thus composites of strong
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Characterizing Compounds using IR
Spectra
IR characterization requires a systematic survey of the peak ID &
fingerprint regions and identify certain clues on the presence or
absence of certain group frequencies characterizing a particular
functional group.
Examine the fingerprint region (1500 - 600 cm-1 ) and the overall
spectrum to tentatively assign structures by matching peak for
peak.
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Fig.29. Correlation Chart 1:
Typical IR Absorption Ranges of Common bonds
Short Long
Fig.30 Correlation Chart 2: General Regions of IR Spectrum
(Vibrational bands)
Keys:
Blue colored bands refer to stretching vibrations, and
Green colored band refer to bending vibrations
Group Frequencies
Note that, from the color scheme in Chart 2, stretching
absorptions are in the blue shaded region; bending absorptions in
the green shaded region.
Since most organic compounds have C-H bonds, a useful rule is that
absorption in the
2850 - 3000 cm-1 is due to sp3 C-H stretching;
above 3000 cm-1 is from sp2 C-H stretching or sp C-H stretching
if it is near 3300 cm-1.
Note that,
Complexity of the IR spectra in the 1450 - 600 cm-1
(fingerprint region) makes it difficult to assign all the absorption
bands
because of existence of unique patterns in this region.
Absorption bands in the 4000 - 1450 cm-1 region are due to
stretching vibrations of diatomic units, (also known as group
frequency region).
Identifying Group Frequencies in IR
The H-Stretching Frequency Range (3700 – 2700 cm-1)
In this range:
The H-X stretching vibrations are forming strong
absorption peaks;
The H atom being always the smaller atom than any other
atom forming a bond with it,
the vibrational motion in H-X bond is largely due to the
H-atom;
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The H-X absorption peaks:
Peaks b/n 3000-3100 cm-1 may be largely due to various O-H
& N-H stretching vibrations;
O-H bands are often broader and usually appear at higher
frequencies than N-H bands;
O-H bands are noticed only in the case of dilute non-polar
solvents;
H-bonding tends to broaden the O-H peaks and also move
them towards the lower wave numbers (i.e., longer ’s)
Aliphatic C-H vibration peaks occur in the range of 3000 –
2850 cm-1;
Any substituent that affects the C-H bond strength (e.g., Cl-
C-H) will cause a shift in the C-H Amax beyond 3000 cm-1;
The aldehydic C-H vibration (i.e., in H-C=O) forms a distinct
peak in the range of 2745 – 2710 cm-1;
Substituting D for H causes a shift to the lower wave number
by the factor of approx. 1/√2. (effect used to identify C-H
bonds);
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Identifying Group Frequencies in IR ……..
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Identifying Group Frequencies in IR …….
Double-bond Absorption Range (1950 – 1550 cm-1):
The carbonyl (CO) stretching vibration is characterized by
absorption throughout this region.
The absorption peaks at about 1700 cm-1 are due to the presence
of ketones, aldehydes, acids, amides and carbonates;
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Identifying Group Frequencies in IR …….
Note that,
a strong C-O-R stretching peak is obtained at about 1200
cm-1 in case of esters, while
a distinct H-C- peak is obtained just above 2700 cm-1 in case
of aldehydes;
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Identifying Group Frequencies in IR ……..
The fingerprint region (1500 – 600 cm-1).
This region constitutes strong evidences for the identities of cpds.
Bands in this region are due to single bonds which are nearly of
similar energies;
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Fig.31: A Correlation Chart for IR Spectroscopy
Table 2: Some easily recognizable IR Absorption
Patterns
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Fig. 32 Assigning Group Frequencies to the
Compound
Fig. 33.Try to associate the spectrum below to any one of
the isomers following it.
Practice Problems on IR
Spectroscopy
Assignment # 3
Find the Worksheets on IR Spectroscopy