NMR spectroscopy is a powerful tool for determining organic structures. It analyzes the magnetic properties of certain nuclei, such as 1H, 13C, 15N, and 31P. When placed in an external magnetic field, nuclei with spin will align either with or against the field. Absorption of photons causes the nuclei to flip alignment. The chemical environment around each nucleus shields it from the field to varying degrees, causing signals to occur at different frequencies. NMR spectra provide information on a molecule's functional groups, number of equivalent protons or carbons, and connectivity between atoms.
NMR spectroscopy is a powerful tool for determining organic structures. It analyzes the magnetic properties of certain nuclei, such as 1H, 13C, 15N, and 31P. When placed in an external magnetic field, nuclei with spin will align either with or against the field. Absorption of photons causes the nuclei to flip alignment. The chemical environment around each nucleus shields it from the field to varying degrees, causing signals to occur at different frequencies. NMR spectra provide information on a molecule's functional groups, number of equivalent protons or carbons, and connectivity between atoms.
NMR spectroscopy is a powerful tool for determining organic structures. It analyzes the magnetic properties of certain nuclei, such as 1H, 13C, 15N, and 31P. When placed in an external magnetic field, nuclei with spin will align either with or against the field. Absorption of photons causes the nuclei to flip alignment. The chemical environment around each nucleus shields it from the field to varying degrees, causing signals to occur at different frequencies. NMR spectra provide information on a molecule's functional groups, number of equivalent protons or carbons, and connectivity between atoms.
NMR spectroscopy is a powerful tool for determining organic structures. It analyzes the magnetic properties of certain nuclei, such as 1H, 13C, 15N, and 31P. When placed in an external magnetic field, nuclei with spin will align either with or against the field. Absorption of photons causes the nuclei to flip alignment. The chemical environment around each nucleus shields it from the field to varying degrees, causing signals to occur at different frequencies. NMR spectra provide information on a molecule's functional groups, number of equivalent protons or carbons, and connectivity between atoms.
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Nuclear Magnetic
Resonance Spectroscopy
Introduction NMR is the most powerful tool available for organic structure determination. It is used to study a wide variety of nuclei: 1H 13C 15N 19F 31P => Chapter 13
In quantum mechanics, spin is an intrinsic property of
all elementary particles. Fermions, the particles that constitute ordinary matter, have half-integer spin 3
Chapter 13
Chapter 13
Nuclear Spin A nucleus with an odd atomic number or an odd mass number has a nuclear spin. The spinning charged nucleus generates a magnetic field.(Intrinsic angular momentum)
Chapter 13
=>
External Magnetic Field
When placed in an external field, spinning protons act like bar magnets.
=> Chapter 13
Two Energy States
The magnetic fields of the spinning nuclei will align either with the external field, or against the field. A photon with the right amount of energy can be absorbed and cause the spinning proton to flip. => Chapter 13
Chapter 13
E and Magnet Strength
Energy difference is proportional to the magnetic field strength. E = h = h B0 2 Gyromagnetic ratio, , is a constant for each nucleus (26,753 s-1gauss-1 for H). In a 14,092 gauss field, a 60 MHz photon is required to flip a proton. It is the ratio of its magnetic dipole moment and angular momentum
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Magnetic Shielding If all protons absorbed the same amount of energy in a given magnetic field, not much information could be obtained. But protons are surrounded by electrons that shield them from the external field. Circulating electrons create an induced magnetic field that opposes the external magnetic field. => Chapter 13
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Shielded Protons Magnetic field strength must be increased for a shielded proton to flip at the same frequency.
=> Chapter 13
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Protons in a Molecule Depending on their chemical environment, protons in a molecule are shielded by different amounts.
Chapter 13
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NMR Signals The number of signals shows how many different kinds of protons are present. The location of the signals shows how shielded or deshielded the proton is. The intensity of the signal shows the number of protons of that type. Signal splitting shows the number of protons on adjacent atoms. => Chapter 13
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The NMR Spectrometer
magnet
RF probe
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The NMR Graph
Chapter 13
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CH3 H3C
Si CH3 CH3
Tetramethylsilane
TMS is added to the sample.
Since silicon is less electronegative than carbon, TMS protons are highly shielded. Signal defined as zero. Organic protons absorb downfield (to the left) of the TMS signal. => Chapter 13
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Chemical Shift Measured in parts per million. Ratio of shift downfield from TMS (Hz) to total spectrometer frequency (Hz). Same value for 60, 100, or 300 MHz machine. Called the delta scale. => Chapter 13
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Delta Scale
Chapter 13
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=>
Spin-Spin Splitting Nonequivalent protons on adjacent carbons have magnetic fields that may align with or oppose the external field. This magnetic coupling causes the proton to absorb slightly downfield when the external field is reinforced and slightly upfield when the external field is opposed. All possibilities exist, so signal is split. => Chapter 13
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Location of Signals More electronegative atoms deshield more and give larger shift values. Effect decreases with distance. Additional electronegative atoms cause increase in chemical shift. => Chapter 13
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Typical Values
Chapter 13
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Carboxylic Acid Proton, 10+
Chapter 13
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Number of Signals Equivalent hydrogens have the same chemical shift.
Chapter 13
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Intensity of Signals The area under each peak is proportional to the number of protons. Shown by integral trace.
Chapter 13
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How Many Hydrogens?
When the molecular formula is known, each integral rise can be assigned to a particular number of hydrogens.
Chapter 13
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=>
Range of Magnetic Coupling Equivalent protons do not split each other. Protons bonded to the same carbon will split each other only if they are not equivalent. Protons on adjacent carbons normally will couple. Protons separated by four or more bonds will not couple. => Chapter 13
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Coupling Constants Distance between the peaks of multiplet Measured in Hz Not dependent on strength of the external field Multiplets with the same coupling constants may come from adjacent groups of protons that split each other. => Chapter 13
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Values for Coupling Constants
=> Chapter 13
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Carbon-13
C has no magnetic spin.
13C has a magnetic spin, but is only 1% of the carbon in a sample. The gyromagnetic ratio of 13C is one-fourth of that of 1H. Signals are weak, getting lost in noise. Hundreds of spectra are taken, averaged. => 12
Chapter 13
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Combined 13C and 1H Spectra
Chapter 13
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Interpreting 13C NMR
The number of different signals indicates the number of different kinds of carbon. The location (chemical shift) indicates the type of functional group. The peak area indicates the numbers of carbons (if integrated). The splitting pattern of off-resonance decoupled spectrum indicates the number of protons attached to the carbon. => Chapter 13
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 5: Gravitational and Inertial Control, #5
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 2: Gravitational and Inertial Control, #2
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 3: Gravitational and Inertial Control, #3
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 4: Gravitational and Inertial Control, #4
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 5: Gravitational and Inertial Control, #5
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 2: Gravitational and Inertial Control, #2
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 3: Gravitational and Inertial Control, #3
Negative Mass and Negative Refractive Index in Atom Nuclei - Nuclear Wave Equation - Gravitational and Inertial Control: Part 4: Gravitational and Inertial Control, #4
