Koradiya Ketan N. Inorganic Chemistry, Reg.

roll No-5, Bhavnagar University, Bhavnagar-05

Introduction 
Nuclear magnetic resonance, or NMR

involves the study of what occurs when the nuclei of certain atoms are placed in

a static magnetic field and exposed to a second changing magnetic field. field.

Spin States
y A nucleus with an odd atomic number or an odd mass

number has a nuclear spin

y The number of allowed spin states is quantized, and is

determined by its spin quantum number, I

y There are 2I+1 allowed spin states

Nuclei with I = 0 have only one spin state and are NMR inactive. These include 12C and 16O, two of the most common nuclei in organic compounds. Nuclei with odd mass numbers have half-integer spin quantum numbers. i.e. 13C, 1H, 31P are spin I = 1/2 17O is spin I = 5/2

A spinning nucleus with a spin quantum number of ½ has 2 possible spin states. 2I+1 = 2 (1/2) + 1 = 2

+

+

Q + 1/2
TWO SPIN STATES

- 1/2

The Most Interesting Elements (to us) All Have 2 Allowed Spin States These are ‡1H ‡13C ‡19F ‡31P Deuterium 2H is spin active with I = 1! 2 (1) + 1 = 3 spin states for deuterium

The spinning of the nuclei causes them to behave like magnets These nuclear magnets are influenced by other magnetic fields. These other magnetic fields may be externally applied or they can be generated by other nearby nuclei or electrons in the molecule. Externally applied magnetic fields may result from the magnet that the sample is placed in or from irradiation by radio frequency light.

External Magnetic Field
When placed in an external field, spinning protons act like bar magnets.

can align either with or against the field, with slight excess of nuclei aligned with the field

In an Applied Magnetic Field Nuclei with 2 allowed spin states

The nuclei precess about an axis parallel to the applied magnetic field, with a frequency called the Larmor Frequency (w)

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.

In an applied magnetic field the spin states have different energies and therefore different populations. quantized
Opposed

-1/2

-1/2

(E = hR +1/2
Radiofrequency

+1/2

(E and Magnet Strength
Energy difference is proportional to the magnetic field strength. (E = hR = K h B0 2T Gyromagnetic ratio, K, 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. Low energy, radio frequency.

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.

Shielded Protons
Magnetic field strength must be increased for a shielded proton to flip at the same frequency.

=>

Protons in a Molecule
Depending on their chemical environment, protons in a molecule are shielded by different amounts.

=>

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.

The NMR Spectrometer

NMR Spectrometer
RF (60 MHz) Oscillator Transmitter
hR absorption signal

RF Detector Receiver

Recorder

MAGNET

MAGNET

N

S

Probe

1) The sample tube is placed in a strong magnetic field to produce the primary splitting of the energy levels and create the necessary population imbalance. The sample is irradiated with a range of radio frequency light to transfer nuclei from the lower to the higher energy state. 3) The oscillating magnetic fields produced by the nuclei are observed using the same coil that was used for the irradiation. A complex, decaying signal is observed that contains all of the information about the nuclei. This is called the free induction decay (FID)
2)

How does our NMR observe the signals?

4) A Fourier transform is performed on the FID to produce an NMR spectrum with each signal represented by a peak at its relative Larmar frequency which is the frequency with which it wobbles as it spins. This is actually done several times and the results are added to increase the signal to noise ratio.

Tetramethylsilane
CH3 H3C Si CH3 CH3

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.

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.

Delta Scale

Location of Signals
y More electronegative

atoms deshield more and give larger shift values. y Effect decreases with distance. y Additional electronegative atoms cause increase in chemical shift. =>

Aromatic Protons, H7-H8

Vinyl Protons, H5-H6

Acetylenic Protons, H2.5

Aldehyde Proton, H9-H10

Electronegative oxygen atom

Chemical shift depends on concentration.

O-H and N-H Signals

Hydrogen bonding in concentrated solutions deshield the protons, so signal is around H3.5 for N-H and H4.5 for O-H. Proton exchanges between the molecules broaden the peak.

Carboxylic Acid Proton, H10+

Number of Signals
Equivalent hydrogen's have the same chemical shift.

Intensity of Signals
The area under each peak is proportional to the number of protons. Shown by integral trace.

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.

1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.

Doublet: 1 Adjacent Proton

Triplet: 2 Adjacent Protons

The N + 1 Rule
If a signal is split by N equivalent protons, it is split into N + 1 peaks.

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.

Splitting for Ethyl Groups

Splitting for Isopropyl Groups

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