Spectroscopy
Infrared Spectroscopy
• Measures molecular vibrations which can be seen as bond stretching, bending or
combinations of different vibrational modes.
Intramolecular Vibrations and Rotations
• Infrared light range has a wavelength range of: 700 nm to 1 mm
o Useful absorptions occur at wavelengths between 2500 to 25,000 nm.
• Wavenumber: like the frequency but in units of cm-1. 𝑊𝑎𝑣𝑒𝑛𝑢𝑚𝑏𝑒𝑟 = 1/𝜆
• When light with wavenumbers between 4000 to 400 cm-1 is absorbed, the molecules
enter an excited vibrational states.
o Four types can occur: Symmetric bend, asymmetric bend, symmetric stretch,
asymmetric stretch
• Fingerprint Region: wavenumbers in range of 1500 to 400 cm-1 where complex vibration
patters occur. Patterns are associated with the motion of the molecule as a whole.
• For the absorption to be recorded, the vibration must result in a change in the bond
dipole moment.
o Molecules with same electronegativity (O2 & Br2) are not useful, neither are
symmetric molecules like C2H2.
Characteristic Absorptions
• Can be used to identify the functional groups. Most important peaks to know are:
o Hydroxyl (O-H): absorbs wide peak at 3300 cm-1 for alcohols and 3000 cm-1 for
carboxylic acids.
o Carbonyl (C double bonded to O): sharp peak at 1700 cm-1
o N-H Bonds: have a sharp peak at 3300 cm-1
• Bond between any atom and hydrogen always has a high absorption frequency
• As more bonds are added between carbon atoms, the absorption frequency increases
• All frequencies in the fingerprint region are out of scope.
• Transmittance: amount of light that passes through the sample and reaches the
detector
• IR spectra is plotted as Transmittance vs wavenumber
Ultraviolet Spectroscopy
• UV spectra are obtained by passing ultraviolet light through a sample that is usually
dissolved in an inert, non-absorbing solvent, and absorbance is caused by the electron
transitions between orbitals.
• Most important information gathered: wavelength of the maximum absorbance
o Can tell us the extent of conjugation within the system
o As conjugation increases, the energy lowers and thus the wavelength increases.
Electron Transitions
• UV spectroscopy works because molecules with pi-bonds or nonbonding electrons can
be excited by UV light to high energy orbitals
• Molecules with a lower gap between the highest occupied molecular orbital (HOMO)
and the lowest occupied molecular orbital (LUMO) are more easily excited and can thus
absorb longer wavelengths.
Conjugated Systems
• Conjugated molecules are molecules with unhybridized p-orbitals
• These can be excited by UV light
• Conjugation causes a shift in the absorption spectrum that results in higher maximum
wavelengths.
Nuclear Magnetic Resonance Spectroscopy
• NMR: the most important spectroscopic technique on the MCAT
o Certain atomic nuclei have magnetic moments that are oriented at random, but
when placed in a magnetic field, the moments of these nuclei tend to align with
the field or opposite to the field.
▪ Nuclei with magnetic moments that are aligned with the field are in the
alpha state
o From the alpha state, radiofrequency pulses can be radiated onto the nuclei to
excite the lower energy nuclei into the Beta-state.
o Absorption of radiation leads to excitation at different frequencies
• MRI: a non-invasive diagnostic tool that uses proton NMR
• NMR Spectrum: plot of frequency vs absorption of energy
o Standardized method uses a chemical shift () with units of ppm of
spectrometer frequency.
▪ This is plotted on the x-axis and increases to the left (downfield)
o Tetramethylsilane (TMS) is used as a calibration standard to mark the location of
0 ppm
• Can be conducted on any atom which possesses a nuclear spin (odd mass number or
odd atomic number or both)
Proton NMR (1H-NMR)
• Most hydrogens come into resonance from 0 to 10 ppm downfield from TMS
• Protons that are chemically equivalent will have the same magnetic environment and
will thus correspond to the same peak.
• Height of each peak is proportional to the number of protons.
• Deshielding: the more a protons electron density is pulled away (by more
electronegative elements), the less it can shield itself from the applied magnetic field.
• Spin-Spin Coupling (splitting): when two protons are in close proximity but are not
magnetically identical.
o Results in a doublet being formed: two peaks of identical intensity, equally
spaced around the true chemical shift of a proton.
o n+1 Rule: if a proton has n protons that are three bonds away, it will split into
n+1 peaks
▪ Do not include protons attached to oxygen or nitrogen
o Magnitude of splitting is called the coupling constant, J.
• Chemical Shift ranges:
o Deshielded aldehyde: 9-10 ppm
o Carboxylic acid: 10.5-12 ppm
o Hydrogen on Aromatic Ring: 6.0-8.5 ppm
o Sp3 Hybridized carbons: 0-3 ppm
o Sp2 Hybridized carbons: 4.6-6.0 ppm
o Sp Hybridized carbons: 2.0-3.0 ppm
o When electronegative groups are present, they pull electron density away from
the proton and further deshield it.