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    Lecture IR4

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    Gerges Samir
    This document discusses factors that affect the frequency of infrared peaks, including: 1. Resonance, conjugation, and symmetry which can lower frequencies. 2. Ring strain which increases carbonyl and C-H stretching frequencies in smaller rings. 3. Halogens which increase carbonyl and C-H stretching frequencies when bonded. 4. Chirality which can cause frequency splitting between enantiomers and conglomerates. 5. Phase (solid, liquid, gas) with fundamentals shifted to higher frequencies in gases and effects of hydrogen bonding in liquids.

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    Lecture IR4

    Uploaded by

    Gerges Samir
    13 views58 pages
    This document discusses factors that affect the frequency of infrared peaks, including: 1. Resonance, conjugation, and symmetry which can lower frequencies. 2. Ring strain which increases carbonyl and C-H stretching frequencies in smaller rings. 3. Halogens which increase carbonyl and C-H stretching frequencies when bonded. 4. Chirality which can cause frequency splitting between enantiomers and conglomerates. 5. Phase (solid, liquid, gas) with fundamentals shifted to higher frequencies in gases and effects of hydrogen bonding in liquids.

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    This document discusses factors that affect the frequency of infrared peaks, including: 1. Resonance, conjugation, and symmetry which can lower frequencies. 2. Ring strain which increases carbonyl and C-H stretching frequencies in smaller rings. 3. Halogens which increase carbonyl and C-H stretching frequencies when bonded. 4. Chirality which can cause frequency splitting between enantiomers and conglomerates. 5. Phase (solid, liquid, gas) with fundamentals shifted to higher frequencies in gases and effects of hydrogen bonding in liquids.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    13 views58 pages

    Lecture IR4

    Uploaded by

    Gerges Samir
    This document discusses factors that affect the frequency of infrared peaks, including: 1. Resonance, conjugation, and symmetry which can lower frequencies. 2. Ring strain which increases carbonyl and C-H stretching frequencies in smaller rings. 3. Halogens which increase carbonyl and C-H stretching frequencies when bonded. 4. Chirality which can cause frequency splitting between enantiomers and conglomerates. 5. Phase (solid, liquid, gas) with fundamentals shifted to higher frequencies in gases and effects of hydrogen bonding in liquids.

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    © All Rights Reserved
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    of 58

    Factors affecting the frequency of infrared peaks

    1. Resonance, symmetry and conjugation


    Effect of resonance, symmetry and conjugation on infrared
    frequencies O- O
    + +
    N N

    O O -

    O- O
    C C

    O O -

    +
    NR2 NR2
    C C

    O O -

    What about the effect of conjugation?


    +

    O O-

    Do the facts support this interaction?


    O- O
    C C

    O O -

    Carbonyl frequency: 1720-1680 (acid)  1700 cm-1


    Ether frequency = 1000 to 1400 cm-1  1200 cm-1

    Average of the two fundamentals = 1450 cm-1


    1560 cm-1 1410 cm-1

    O- O (1560+ 1410)/2 = 1485 cm-1


    C C

    O O -
    Resonance

    100

    80
    % Transmittance

    60

    40

    20
    1550 1400
    0
    4000 3500 3000 2500 2000 1500 1000 500
    Wavenumbers, cm-1

    Figure IR-42. Sodium benzoate, KBr pellet:


    Sodium benzoate: (1550, 1400 cm-1 ); Average : 1475 cm-1
    Sodium acetate: (1560, 1410 cm-1 ); Average : 1485 cm-1
    O O-

    R NR2 R NR2+

    How important is resonance in amides?


    CH3 CH3
    N C
    CH3 O
    O O-

    R NR2 R NR2+

    How important is resonance in amides?


    O
    CH3
    In H N
    the barrier to rotation of the two
    CH3 CH3 groups is approximately 18
    kcal/mol

    (A C-C  bond is worth about 60 kcal/mol)


    Table 4. The effect of conjugation on carbonyl frequencies.

    Non-conjugated Frequency Conjugated Frequency Frequency


    Compound cm -1 Compound cm -1 cm -1

    butanal 1725 2-butenal 1691 benzaldehyde 1702

    2-butanone 1717 methyl vinyl 1700, acetophenone 1685


    ketone 1681

    propanoic acid 1715 propenoic acid 1702 benzoic acid 1688

    ethyl propionate 1740 ethyl acrylate 1727 ethyl benzoate 1718

    butanoic anhydride 1819, 2-butenoic 1782, benzoic 1786,


    1750 anhydride 1722 anhydride 1726

    cis-cyclohexane- 1857, 1-cyclohexene- 1844, phthalic 1852,


    1,2-dicarboxylic 1786 1,2-dicarboxylic 1767 anhydride 1762
    anhydride anhydride
    Other effects of conjugation on carbonyl frequencies

    100

    80
    % Transmittance

    60

    40

    20

    0
    4000 3500 3000 2500 2000 1500 1000 500
    Wavenumbers, cm-1

    Figure IR-45. Ethyl vinyl ketone, neat liquid: CH3CH2COCH=CH2


    100

    80
    % Transmittance

    60

    40

    20

    0
    4000 3500 3000 2500 2000 1500 1000 500
    Wavenumbers, cm-1

    Figure IR-44. 3-Nonen-2-one, 95%; neat liquid, thin film:

    Why the extra carbonyl peaks? CH3 CH=CH(CH2)4CH3


    O
    O

    Factors affecting the intensities : Extent of interaction (dipole


    moment change)
    Concentration of each conformer

    O O-
    Overtones in terminal olefins
    What’s
    this?
    1804 cm-1
    1796 cm-1
    Factors affecting the frequency of infrared peaks
    1. Resonance and conjugation
    2. Ring strain:
    A: on carbonyl frequencies
    1720 cm-1

    1750 cm-1

    1775 cm-1

    cyclopropanone
    1800 cm-1
    Table. The Effect of Ring Strain on the Carbonyl Frequencies of
    Some Cyclic Molecules

    Ring Size ketone: cm-1 lactone: cm-1 lactam: cm-1


    3 cyclopropanone: 1800
    4 cyclobutanone: 1775 -propiolactone: 1840
    5 cyclopentanone: 1751 -butyrolactone: 1750 -butyrolactam: 1690
    6 cyclohexanone: 1715 -valerolactone: 1740 -valerolactam: 1668
    7 cycloheptanone: 1702 caprolactone: 1730 caprolactam: 1658
    Factors affecting the frequency of infrared peaks
    1. Resonance and conjugation
    2. Ring strain:
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    What is the hybridization of a C-H bond in cyclopropane?
    CH2OH
    CH2OH
    Factors affecting the frequency of infrared peaks
    1. Resonance and conjugation
    2. Ring strain:
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    3. Halogens
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    3011

    1760
    1754,1783 cm-1
    Factors affecting the frequency of infrared peaks
    1. Resonance and conjugation
    2. Ring strain:
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    3. Halogens
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    4. Chirality
    Why the big differences between D-serine and DL-serine?
    d l d

    d l
    Some Examples of Conglomerates
    Asparagine
    Threonine
    Glutamic Acid
    Serine Anhydride
    N-Acetylproline
    Factors affecting the frequency of infrared peaks
    1. Resonance and conjugation
    2. Ring strain:
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    3. Halogens
    A: on carbonyl frequencies
    B. on C-H stretching frequencies
    4. Chirality
    5. Phase: solid, liquid and gas (fundamentals in the gas phase are
    shifted to higher frequencies) ie. solvent or solute interactions
    lead to weakening of force constants; effects of H-bonding.
    Effects of H-bonding

    120
    Vapor phase spectrum(135 °C)
    100

    80
    % Transmittance

    liquid film
    60

    40

    20

    0
    4000 3500 3000 2500 2000 1500 1000
    Wavenumbers, cm-1

    Figure IR-25. The liquid and vapor spectra of phenol. OH


    Gas Phase FT-IR spectrum of 2,4-pentanedione, Aldrich Chemical Co.
    Effect of Phase

    Liquid film
    Effect of Phase

    CCl4 solution
    Effect of Phase

    KBr
    Effects of H-bonding

    2000 1000
    cm-1
    FT IR
    ATR: attenuated total reflectance; when a beam of electromagnetic
    radiation is reflected off an object, it actually penetrates of
    the order of one wavelength.
    In IR, this is of the order of microns which is sufficient to
    obtain a spectrum of the material provided it is poly-
    dispersed.
    The depth of penetration is wavelength dependent, it is
    therefore necessary to compensate for this dependency.
    11

    10

    8
    Single Beam

    4000 3000 2000 1000


    Wavenumbers (cm-1)

    Infrared spectrum of ATR and of the background CO2 and H2O


    vapor.

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