How to Determine Proton NMR Shifts

Proton NMR (nuclear magnetic resonance) shifts incorporate magnetism and quantum physics. Protons respond to a magnetic field with two distinct energies, depending on proton spin direction. An induced magnetic field further influences energy levels. Nearby atoms deplete (de-shield) or add to the influential electron cloud around a given proton. Chemical shift can be calculated in terms of ppm (parts per million). Signals often split because of asymmetrical protons interacting with each other. The area on an NMR graph enclosed by a given NMR signal is proportional to how many protons resonate at a given frequency--therefore, at a given PPM value. Although NMR signals look like vertical lines, they are in fact (narrow) bell curves that enclose a finite area.

Things You'll Need

  • Calculator
  • Pen/pencil and scratch paper
  • Periodic table or other chart displaying electronegativity trends and values
  • NMR instrument and equipment, or experimental data containing NMR graphs and magnetic field intensity
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Instructions

    • 1

      Understand how protons respond to magnetic fields. Protons aligning with a magnetic field are in a lower energy state than those "facing" it. The concept is similar to swimming with the current--it takes far less energy than swimming against it. If an external magnetic field has strength B and proton magnetic moment is u, then the difference in energy (E) between spin states is E = uB/I. Variable I is particle spin state. For protons, I = 1/2. Protons have a magnetic moment of 1.41e-26 J/T (Joules/Tesla). A magnetic field strength of 2.35 T would induce an energy difference of 1.41e-26 * 2.35 / (1/2) = 1.41e-26 J/T * 4.7 T = 6.627e-26 Joules.

    • 2

      Account for an induced magnetic field. An external magnetic field (Bext) induces a smaller "counterfield" around a proton (Bcounter). The effective magnetic strength "felt" by a proton (B) is determined by subtracting the counter-field: B = Bext - Bcounter.

    • 3

      Rank nearby atoms by electron affinity. Protons in CH3Cl (chloromethane) register at 3.05 ppm. Since chlorine (Cl) is more electronegative than bromine (Br), it would be expected that CH3Br (bromomethane) would have slightly lower ppm values. Indeed, CH3Br reaches the hydrogen proton peak at 2.682 ppm.

    • 4

      Calculate expected chemical shift (S). S = (v - v0)/v0, where v is the resonant proton frequency in question. Variable v0 is a reference proton frequency. The NMR signal from tetramethylsilane (TMS) defines the v0 reference peak. Protons more shielded by electrons than hydrogen protons in TMS show up with negative ppm. Resonant proton frequencies v and v0 are calculated using quantum mechanics.

    • 5

      Account for split signals. Split signals are separated by coupling constant J. J-value depends on molecular geometry (dihedral angle a) and experimental parameters A, B, and C in the form J = A + Bcos(a) + Ccos(2*a). Lower temperature may reveal signal splitting since lower temperatures correspond to less noise in data gathered by NMR spectroscopy.

    • 6

      Integrate peak areas. Integrated NMR peaks provide relative amounts of each structural "type" of proton. If a molecule contains several equivalent protons, as in CH4, then there will be one peak. If there are two proton types, as in CH3CHO, two peaks will show up. One peak would correspond to the hydrogen in "CHO" and will enclose a certain area. Another peak, corresponding to the three hydrogen protons in "CH3" would enclose an area three times as large as the "CHO" hydrogen peak.

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