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Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy 1

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Page 1: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Structure Determination by Spectroscopy

Mass spectroscopy

Ultraviolet-visible spectroscopy

Infrared spectroscopy

Nuclear magnetic resonance spectroscopy

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Page 2: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Mass Spectroscopy Mass spec gives information about the molecular weight, and thus

the formula, of a molecule.

A sample is vaporized and bombarded with high energy electrons. The impact ejects an electron from the sample to give a radical cation.

A-B [A.B]+. + e-

The cation is detected and recorded as the M+ (molecular cation) peak, usually the highest mass peak in the spectrum.

The M+ peak gives the molecular weight of the compound.

The mass / charge (m/z) ratio is always an even number except when the molecule contains an odd number of Nitrogen atoms.

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Page 3: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Mass Spectroscopy Isotopes have different atomic weights and

so can be separated by the spectrometer.

Halogens can be identified by their isotope ratios. 35Cl and 37Cl in a 3:1 ratio 79Br and 81Br in a 1:1 ratio 127I is the natural isotope

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Page 4: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Mass Spectroscopy The radical cation can fragment to a radical

(no charge) and a cation.

[A.B]+. A + B+ or A+ + B

Only the cations are detected in the mass spectrometer. The most intense peak is called the “Base Peak”, which is

arbitrarily set to 100% abundance; all other peaks are reported as percentages of abundance of “Base Peak.”

Different groups of atoms will fragment in characteristic ways.

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Page 5: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Interaction of electromagnetic radiation energy and matter When EMR is directed at a substance, the

radiation can be:

Absorbed Transmitted Reflected

depending on the frequency (or wavelength or energy) of the radiation and the structure of the substance.

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Page 6: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Electromagnetic Radiation

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Page 7: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Mathematical Relationships

E = hc / E = hc =

= Frequency (Hz) c = Velocity of Light (3 x 1010 cm/sec)

= Wavelength (cm) h = Planck’s Constant (6.62 x 10-27 erg-sec)

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Page 8: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Interaction of electromagnetic radiation energy and matter

Molecules exist only in discrete states that correspond to discrete energy content.

The EMR energy that is absorbed is quantized and brings about certain specific changes in the molecule. electronic transitions (UV-vis) vibrations (IR) rotations (IR)

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Page 9: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Interaction of electromagnetic radiation energy and matter

Exact energies absorbed by a molecule are highly characteristic of the structure and are unique for each compound. spectroscopic “fingerprint”

Similar functional groups absorb similar energies regardless of the structure of the rest of the compound.

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Page 10: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

UV-visible Spectroscopy Ultraviolet: 200 nm – 400 nm Visible: 400 nm – 800 nm Most organic molecules and functional groups do not absorb

energy in the UV-visible part of the EMR spectrum and thus, absorption spectroscopy in the ultraviolet-visible range is of limited utility.

When a molecule does absorb in the UV-vis, the energy transitions that occur are between electronic energy levels of valence electrons, that is, electrons in orbitals of lower energy are excited to orbitals of higher energy.

Energy differences generally of 30 –150 kcal/mole

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Page 11: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

UV-visible Spectroscopy The ground state of an organic molecule can contain valence

electrons in three principal types of molecular orbitals:

C::C

C : H (sigma)

(pi)

n (non-bonding)

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Page 12: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

UV-visible Spectroscopy Electrons in sigma bonds (single bonds) are too tightly bound

to be promoted to a higher energy level by UV-visible radiation.

alkanes, alcohols, alkyl halides, simple alkenes do not absorb in the UV

Electrons in pi bonds and non-bonding orbitals are more loosely held and can be more easily promoted.

Conjugation of pi bonds lowers the energy of the radiation that is absorbed by a molecule.

Conjugated unsaturated systems are molecules with two or more double or triple bonds each alternating with a single bond.

If a molecule does not absorb in the UV, then it does not contain a conjugated system of alternating double bonds or a carbonyl group.

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Page 13: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Infrared Spectroscopy Infrared

Almost all organic compounds absorb in this region between the visible and radiowaves

800 nm (12,500 cm-1) to 107 nm (1.0 cm-1)

Area of greatest interest in organic chemistry is the vibrational portion 2,500 nm (4,000 cm-1) to 15,000 nm (~700 cm-1)

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Page 14: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Infrared Spectroscopy Radiation in the vibrational infrared region is

expressed in frequency units called wave numbers, which are the reciprocal of the wavelength () expressed in centimeters.

(cm-1) = 1 / (cm) (cm-1) = (nm-1) x 107

Wave numbers can be converted to energy by multiplying by hc. Thus wave numbers are proportional to energy.

hchcE ν/

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Page 15: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Infrared Spectroscopy Molecular Vibrations

Absorption of infrared radiation corresponds to energy changes on the order of 8-40 kJ/mole (2-10 kcal/mol)

The frequencies in this energy range correspond to the stretching and bending frequencies of covalent bonds, that is, changes in bond length and in bond angle, respectively.

Two uses for IR: IR spectra can be used to distinguish one compound from

another (“fingerprint”) Information about the functional groups present in a

compound

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Page 16: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Infrared Spectroscopy

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Page 17: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Alkane Decane CH3(CH2)8CH3

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Page 18: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Aromatic Isopropylbenzene

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Page 19: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Alkyne 1-Pentyne

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Page 20: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Alcohol 3-Heptanol

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Page 21: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Amine Benzylamine

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Page 22: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Ketone 3-Hexanone

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Page 23: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Aldehyde Hexanal

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Page 24: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Carboxylic acid Proprionic acid

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Page 25: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Ester Methyl benzoate

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Page 26: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Ether Methyl phenyl ether

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Page 27: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Nitrile Butyronitrile

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Page 28: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Nitro compound Nitrobenzene

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Page 29: Structure Determination by Spectroscopy Mass spectroscopy Ultraviolet-visible spectroscopy Infrared spectroscopy Nuclear magnetic resonance spectroscopy

Summary

• Identify functional groups that are present or absent, using Pavia’s sections

• Do not over-analyze an IR spectrum – there is usually complementary information from other sources to identify the compound

• Not every peak can be identified, so don’t try

• Look at lots of examples!

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