What is meant by the term chemical shift?

Chemical shift refers to the difference in resonant frequency between a nucleus and a reference standard, caused by differences in shielding.


Nuclei in different chemical environments will have slightly different resonant frequencies.

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What is the symbol for chemical shift?

δ

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What are the units of chemical shift?

Parts per million (ppm)

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Explain the effect of shielding on chemical shift.

The electrons surrounding a nucleus act to shield it from the external magnetic field. Nuclei that are more shielded by surrounding electrons will experience a weaker magnetic field. This results in a lower resonance frequency and a smaller chemical shift value for more shielded nuclei.


For example, electronegative atoms like oxygen draw electron density away from directly bonded carbon atoms, decreasing their shielding and increasing their chemical shift.

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Why is tetramethylsilane (TMS) used as the standard for chemical shift measurements?

TMS gives a single peak with all 12 hydrogen atoms resonating at the same frequency. This peak is defined as 0 ppm, so TMS provides a reference point to measure other chemical shifts.

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What do the axes of an NMR spectrum represent?

The x-axis represents the chemical shift (δ), measured in ppm.

The y-axis represents the energy absorbed from the radio signal.

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In which direction does chemical shift increase in an NMR spectrum?

Chemical shift increases in value from right to left. 


This means the TMS peak at 0 ppm is always found at the far right of the chemical shift scale.

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What 4 pieces of information does a proton NMR spectrum reveal about the carbon environments in an organic compound?

A proton NMR spectrum reveals:

  1. The number of proton environments.
  2. The types of proton environment present.
  3. The relative numbers of each type of proton.
  4. The number of non-equivalent protons adjacent to a given proton.

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How can you work out the number of proton environments in a molecule from its 1H NMR spectrum?

The number of peaks in the 1H NMR spectrum corresponds to the number of unique proton environments in the molecule.

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How can you work out the types of proton environment present in a molecule from its 1H NMR spectrum?

The chemical shift range that a peak appears in indicates the type of proton environment. Different ranges correspond to different functional groups.

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What information do spin-spin splitting patterns provide?

Spin-spin splitting patterns reveal the number of non-equivalent protons on adjacent carbon atoms.

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What is the n + 1 rule?

For a proton with n protons attached to an adjacent carbon atom, the number of sub-peaks in a splitting pattern = n + 1


For example, a peak split into three (i.e. a triplet) indicates there are two hydrogens on the neighbouring carbon atom. 

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What is a deuterated solvent?

A deuterated solvent is one in which the 1H atoms have been replaced by 2H atoms.


The 2H isotope of hydrogen is called deuterium (D).

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Explain why deuterated solvents are used in 1H NMR spectroscopy.

The 1H atoms in a regular solvent produce signals that can interfere with the spectrum of the sample being analysed.

Deuterium does not produce any signal in the frequency ranges used for 1H, so this interference is prevented and a higher resolution of the sample's spectrum can is obtained.


CDCl3 is a commonly used deuterated solvent in NMR spectroscopy.

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Why are -OH and -NH protons difficult to identify in 1H NMR spectra?

-OH and -NH peaks are often broad and variably shifted due to hydrogen bonding.

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How can you identify the signals produced by -OH and -NH protons in a 1H NMR spectrum using D2O?

  1. To identify -OH and -NH proton signals, compare two 1H NMR spectra: one without D2O and one with D2O added to the sample.
  2. When D2O is added, the -OH and -NH protons exchange with deuterium, which does not produce signals in the 1H NMR range.
  3. As a result, the -OH and -NH peaks present in the first spectrum will disappear in the second spectrum, allowing you to identify these exchangeable protons.

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What is meant by the chemical environment of an atom?

The chemical environment of an atom refers to its position within a molecule, encompassing all atoms, functional groups, and bonds directly connected to the nucleus.

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Why are 1H NMR spectra more complex than 13C NMR spectra?

1H NMR spectra are more complex than 13C NMR spectra due to the presence of spin-spin coupling between hydrogen atoms which causes NMR peaks to split into sub-peaks.

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How can you work out the relative numbers of each type of proton present in a molecule from its 1H NMR spectrum?

The relative peak areas are proportional to the relative numbers of equivalent protons producing each signal.

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