Determination of CHM 3402

Molecular Structures Dr. Mohd Rashidi Abdull Manap

Learning
Outcomes
Students
should be able
to understand:
3-Determination of
molecular structures
 Determination of molecular
structures
• How does FTIR method fit into this process?

Wavenumber
Functional Groups
FTIR
Position (cm-1)
Wavenumber Molecular
shape/ shift environment
Functional Groups Analysis
Calculation of a Molecular Vibrations
• The stretching wavenumbers of C-H can be calculated:https
://www.chromacademy.com/lms/sco533/06-infrared-spectroscopy-ca
lculation-molecular-vibrations.html

• This value (3023 cm-1) is shifted because the calculation does not take
into account the molecular environment of C-H group within the
https://www.chromacademy.com/lms/sco533/06-infrared-spec
molecule troscopy-calculation-molecular-vibrations.html
 IMPORTANCE!

The wavenumbers are depend on the force constants, k of the atoms

 Functional Groups Region Fingerprint Region

N
N

O N
N

FT-IR Spectrum of Caffeine Anhydrous

DOI: 10.1002/cphc.200600308
-Stretching
wavenumbers are
higher than
bending
wavenumbers. 

-Bonds to
hydrogen have
higher
wavenumbers
than those to
heavier atoms.. 
Intensity of the IR peak
• The greater the change in dipole moment, the more intense the IR
absorption

Most Polar Least Polar

O H > N H > C H
Most Intense Least Intense

• Concentration of the analyte (Beer’s Law)

does not possess a permanent dipole moment, so it is
O O not infrared active. (NOT DETECTED IN IR SPECTRUM)
1650 cm−1 (amide I of proteins), Increasing
1536 cm−1 (amide II of proteins), absorbance
trend
moving
from the
stock
1453 cm−1 (CH2 scissoring) solution
(red) to the
highest
concentratio
n of protein
(black)
https://doi.org/10.1016/j.vibspec.2018.08.019
 noise

Weak peaks

Medium peaks

Very strong peaks

Wavenumbers
• Wavenumber decreases with increasing atomic weight
• Wavenumber increases with increasing bond energy

Most Polar Least Polar

O H > N H > C H
Most Intense Least Intense
 ~
𝒗
2900 cm-1

1300 cm-1

Wavenumber decreases with increasing atomic

weight
1250 cm-1
stretching vibrations

1100 cm-1

Heaviest Atoms
 ~
https://doi.org/10.1016/j.jaap.2018.04.002

𝒗
1200 cm-1

1.54 Ang

Wavenumber increases with increasing bond energy

stretching vibrations
?? cm-1
1.34 Ang

2200 cm-1

1.20 Ang
Strongest bond
energy
 ~
𝒗
1100 cm-1

1.43 Ang

stretching vibrations
?? cm-1
1.23 Ang

2087 cm-1

1.13 Ang
Strongest bond
energy
Experimental FTIR Spectrum of H2O (liquid)
Asymmetric Stretching ca 3553 cm-1 Bending ca 1692 cm-1

Symmetric Stretching ca 3412 cm-1

Calculated FTIR Spectrum of H2O in gas phase

C-H3,
C-H2,
C-H,
C-C,
C=C,
N-H,
C-N
FTIR Spectrum of street sample which has been identified as a mixture of Caffeine and l-
Methamphetamine HCl Unpublished manuscript
FTIR Spectrum of street sample which has been identified as a mixture of Caffeine and l-
Methamphetamine HCl Unpublished manuscript
Asymmetric Stretching ca 3553 cm-1 Bending ca 1692 cm-1

Symmetric Stretching ca 3412 cm-1

Take 5 minute

and come back, please

Spectral Assignment Process
Identify X-H Groups Identify Functional Groups Use Fingerprint Region
O-H 3600-3200 (s) C-C ∼1200 (m) Directly match peaks in this region
{often broad} C=C ∼1660 (s)
NH2 3500-3300 (m) C=C (aromatic) ∼1600 (m)
{2 bands} C≣C ∼2200 (w)

C-H(aromatic) 3040-3010 (w) C=O (ester) 1800-1730 (vs)

C-H(alkene) 3095-3010 (m) C=O (aldehyde) 1740-1695 (s)
C-H(alkane) 2960-2850 (m) C=O (ketone) 1735-1660 (s)
C=O (acid) 1725-1680 (vs)
C=O (amide) 1690-1600 (s)

C-N 1380-1080 (mw)

C-O 11150-1070 (s)

3
Hydrocarbons
• Carbon-carbon bonds
• Stronger bonds absorb at higher frequencies:
• C-C 1200 cm-1
• C=C 1660 cm-1
• CC 2200 cm-1 (weak or absent if internal)

• Conjugation lowers the wavenumber:

• isolated C=C 1640 - 1680 cm-1
• conjugated C=C 1620 - 1640 cm-1
• aromatic C=C approx. 1600 cm-1

• Carbon-hydrogen bonds
• Bonds with more s character absorb at a higher wavenumber.
• Alkane (sp3) C-H, just below 3000 cm-1 (to the right)
• Alkene (sp2)C-H, just above 3000 cm-1 (to the left)
• Alkyne (sp) C-H, at 3300 cm-1
Alkanes and Alkenes
Alkynes
O-H and N-H Stretching
Both of these occur around 3300 cm-1, but they look
different.
• Alcohol O-H, broad with rounded tip.
• Secondary amine (R2NH), broad with one sharp spike.
• Primary amine (RNH2), broad with two sharp spikes.
• No signal for a tertiary amine (R3N).
An Alcohol IR Spectrum
Amine IR Spectrum
• Secondary amine (R2NH), broad with one sharp
peak.
• Primary amine (RNH2), broad with two sharp peaks.
Carbon - Nitrogen Stretching
• C - N absorbs around 1200 cm-1
• C = N absorbs around 1660 cm-1 and is much
stronger than the C = C absorption in the same
region
• C  N absorbs strongly just above 2200 cm-1. The
alkyne C  C signal is much weaker and is just
below 2200 cm-1
A Nitrile IR Spectrum
Carbonyl Compounds
• The C=O bond of simple ketones, aldehydes, and carboxylic
acids absorb around 1710 cm-1.
• Usually, it’s the strongest IR signal.
• Carboxylic acids will have O-H also.
An Amide IR Spectrum
A Ketone IR Spectrum
A Carboxylic
• This O-H absorbsAcid
broadly, 2500-3500 cm , due to strong
-1

hydrogen bonding.
An Aldehyde IR Spectrum
• Aldehydes have two C-H signals around 2700 and
2800 cm-1.
Variations in C=O Absorption
• Conjugation of C=O with C=C lowers the stretching
wavenumber to ~1680 cm-1.
• The C=O group of an amide absorbs at an even lower
wavenumber, 1640-1680 cm-1.
• The C=O of an ester absorbs at a higher wavenumber,
~1730-1740 cm-1.
• Carbonyl groups in small rings (5 C’s or less) absorb at
an even higher wavenumber
Strengths and Limitations
• IR alone cannot determine a structure
• IR spectrum is unique to each chemical
structures
• Comparison with a reference spectrum can
confirms the identity of unknown compound
• Modern FTIR spectroscopy is available for a non-
spectroscopist (Police, KKM, Pharmacist)
Thank you