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    IR Spect

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    Manu Sahay
    1) Infrared spectroscopy analyzes molecular vibrations caused by infrared radiation, which can identify functional groups based on their vibrational frequencies. 2) Symmetrical vibrations do not change the dipole moment and are not IR active, while asymmetrical vibrations do change the dipole moment and are IR active. 3) Heavier atoms shift vibrational frequencies to lower wavenumbers, while stronger bonds correspond to higher wavenumbers.

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    IR Spect

    Uploaded by

    Manu Sahay
    55 views15 pages
    1) Infrared spectroscopy analyzes molecular vibrations caused by infrared radiation, which can identify functional groups based on their vibrational frequencies. 2) Symmetrical vibrations do not change the dipole moment and are not IR active, while asymmetrical vibrations do change the dipole moment and are IR active. 3) Heavier atoms shift vibrational frequencies to lower wavenumbers, while stronger bonds correspond to higher wavenumbers.

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    1) Infrared spectroscopy analyzes molecular vibrations caused by infrared radiation, which can identify functional groups based on their vibrational frequencies. 2) Symmetrical vibrations do not change the dipole moment and are not IR active, while asymmetrical vibrations do change the dipole moment and are IR active. 3) Heavier atoms shift vibrational frequencies to lower wavenumbers, while stronger bonds correspond to higher wavenumbers.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    55 views15 pages

    IR Spect

    Uploaded by

    Manu Sahay
    1) Infrared spectroscopy analyzes molecular vibrations caused by infrared radiation, which can identify functional groups based on their vibrational frequencies. 2) Symmetrical vibrations do not change the dipole moment and are not IR active, while asymmetrical vibrations do change the dipole moment and are IR active. 3) Heavier atoms shift vibrational frequencies to lower wavenumbers, while stronger bonds correspond to higher wavenumbers.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 15

    Molecular Vibrations

    and
    IR Spectroscopy
    Vibrations
    What is a vibration in a molecule?
    Any change in shape of the molecule- stretching
    of bonds, bending of bonds, or internal rotation
    around single bonds

    Can a vibration change the dipole moment


    of a molecule? (Shockwave animation)
    Asymmetrical stretching/bending and internal
    rotation change the dipole moment of a molecule.
    Asymmetrical stretching/bending are IR active.

    Symmetrical stretching/bending does not. Not


    IR active
    What wavelength of electromagnetic
    radiation is involved in causing vibrations in
    molecules?
    Infrared (IR) electromagnetic radiation
    causes vibrations in molecules (wavelengths
    of 2500-15,000 nm or 2.5 – 15 µm)

    For a vibration at 4111 cm-1 (the stretch in


    H2), how many vibrations occur in a second?
    120 trillion vibration per second!!!!
    120 x 1012 vibrations/sec or a vibration
    every 8 x 10-15 seconds!
    WOW !!!!!
    How does the mass influence the vibration?

    H2 I2

    MM =2 g/mole
    MM =254 g/mole

    The greater the mass - the lower the wavenumber


    How much movement occurs in the
    vibration of a C-C bond?
    stretching vibration
    154 pm
    For a C-C bond with a bond
    length of 154 pm, the
    variation is about 10 pm.
    10 pm

    bending vibration
    For C-C-C bond angle a
    10 pm
    change of 4o is typical.
    4o
    This moves a carbon
    atom about 10 pm.
    A little physics of
    electromagnetic radiation
    • Energy (E) E = hν = hc/λ = hcν’
    – where h is Planck’s constant, c is the speed of
    light, ν is frequency or the number of vibrations
    per second and λ is the wavelength

    • Wavenumber (ν’) ν’ = 1/ λ
    – given in cm-1

    • Period (P) P = 1/ν


    – the time between a vibration
    Energy, frequency, and wavenumber are directly proportional to each other.
    What type of vibrations would
    occur in pentane?

    Let’s examine the IR spectrum of pentane.


    IR spectrum
    C-H
    stretching C-H
    bending
    Increasing
    absorption of
    IR radiation
    C-C
    bending

    Increasing wavelength

    Increasing wavenumber (energy, frequency)


    IR Spectra of chloroform
    and deuterochloroform
    Increasing absorbance

    Shift of peak due


    to replacement of
    H with D (2x mass)

    Mode of vibration CHCl3 CHCl3 CDCl3


    Calculated* Measured Measured
    C-H stretching 3002 3020 2256
    C-H bending 1120 1219 912
    C-Cl stretching 701 773 737
    C-Cl bending 418 671 652
    * Spartan ’02 AM1 minimization
    Some results
    • Calculated values using computational
    software give lower wave numbers

    • Increasing mass of substituted atoms shifts


    wave numbers to lower values
    (Excel spreadsheet)

    • Stretching energies > bending energies >


    internal rotation energies (occur at higher
    wavelengths)
    Does the stretching energy have
    any relationship to the strength
    of the bond?
    ٥٠٠٠ Wavenumber vs. Bond Energy
    )
    -١

    ٤٠٠٠
    Wavenumber (cm

    ٣٠٠٠
    ٢٠٠٠
    W = 6.3286BE + 401.38
    ١٠٠٠
    r2 = 0.7979
    ٠
    ٢٠٠ ٣٠٠ ٤٠٠ ٥٠٠ ٦٠٠
    Bond energy (kJ/mole)
    Let’s examine the carbonyl group
    on three compounds
    formaldehyde phosgene acetone

    How does the C=O stretching energy compare for


    these three molecules?
    2053 cm-1 1951 cm-1 2063 cm-1
    The carbonyl group has a range of 1700-3000 cm-1.
    Functional group analysis in
    organic compounds

    • Unlike atomic spectroscopy where sharp


    energy transitions occur due to well quantized
    electron transitions, molecular spectroscopy
    tends to show bands.

    • Molecular vibrations are influenced by the


    surrounding groups!
    bending Basic Functional Groups
    C-H

    O-H

    C=O C-O
    stretching

    alkenes
    O-H aromatic

    C-H C C=C C-C


    C

    4000 3000 2000 1000 400

    WAVENUMBER (cm-1)
    Use of IR spectra
    • Identification of functional groups on a
    molecule – this is a very important tool in
    organic chemistry

    • Spectral matching can be done by computer


    software and library spectra

    • Since absorbance follows Beer’s Law, can do


    quantitative analysis

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