In this chapter, we claimed that the NMR signals for \({ }^{2} \mathrm{H}\) (deuterium) and \({ }^{13} \mathrm{C}\) will not overlap \({ }^{1} \mathrm{H}\) spectra. Verify that this statement is true. Show that the frequency \((v)\) will be different for \({ }^{1} \mathrm{H},{ }^{2} \mathrm{H}\), and \({ }^{13} \mathrm{C}\) at a field strength \(\left(B_{0}\right)\) of \(4.7 \mathrm{~T}\). The gyromagnetic ratios for \({ }^{1} \mathrm{H}\), \({ }^{2} \mathrm{H}\), and \({ }^{13} \mathrm{C}\) are \(2.7 \times 10^{8}, 0.41 \times 10^{8}\), and \(0.67 \times 10^{8} \mathrm{rad}\) \(\mathrm{T}^{-1} \mathrm{~s}^{-1}\), respectively.

Short Answer

Expert verified
The frequencies for \( \^{1} \mathrm{H} \) (202.5 MHz), \( \^{2} \mathrm{H} \) (30.7 MHz), and \( \^{13} \mathrm{C} \) (50.1 MHz) are clearly different at 4.7 \mathrm{T}. Therefore, their NMR signals will not overlap.

Step by step solution

01

- Understand the Larmor Frequency Formula

The Larmor frequency is given by \( v = \frac{1}{2\pi} \times \gamma \times B_0 \). Here, \( v \) is the frequency, \( \gamma \) is the gyromagnetic ratio, and \( B_0 \) is the magnetic field strength.
02

- Calculate the Larmor Frequency for \( \^{1} \mathrm{H} \)

Substitute the values for \( \^{1} \mathrm{H} \) into the formula: \( v_{\^{1} \mathrm{H}} = \frac{1}{2\pi} \times 2.7 \times 10^8 \times 4.7 \approx 202.5 \times 10^6 \text{ Hz} \approx 202.5 \text{ MHz} \).
03

- Calculate the Larmor Frequency for \( \^{2} \mathrm{H} \)

Substitute the values for \( \^{2} \mathrm{H} \) into the formula: \( v_{\^{2} \mathrm{H}} = \frac{1}{2\pi} \times 0.41 \times 10^8 \times 4.7 \approx 30.7 \times 10^6 \text{ Hz} \approx 30.7 \text{ MHz} \).
04

- Calculate the Larmor Frequency for \( \^{13} \mathrm{C} \)

Substitute the values for \( \^{13} \mathrm{C} \) into the formula: \( v_{\^{13} \mathrm{C}} = \frac{1}{2\pi} \times 0.67 \times 10^8 \times 4.7 \approx 50.1 \times 10^6 \text{ Hz} \approx 50.1 \text{ MHz} .\).

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Larmor frequency
The Larmor frequency is crucial in NMR Spectroscopy because it tells us the rate at which the nucleus of an atom precesses around the direction of the applied magnetic field. This frequency is unique for each type of nucleus and depends on the magnetic field strength and the gyromagnetic ratio specific to that nucleus.The formula for calculating the Larmor frequency is: \[ v = \frac{\gamma B_0}{2π} \]Here,
  • \(v\) represents the Larmor frequency
  • \(\gamma\) stands for the gyromagnetic ratio
  • \(B_0\) is the magnetic field strength
Understanding how to calculate the Larmor frequency helps in distinguishing between different types of nuclei like
  • \(^{1}H\)
  • \(^{2}H\)
  • \(^{13}C\)
used in NMR experiments.
Gyromagnetic ratio
The gyromagnetic ratio is a fundamental property of nuclei that influences their behavior in a magnetic field. It represents the ratio between the magnetic moment and the angular momentum of the nucleus.Different nuclei have different gyromagnetic ratios influencing their Larmor frequencies. In the given exercise, we used the following gyromagnetic ratios:
  • \(^{1}H\): 2.7 x 10^8 rad T^{-1} s^{-1}
  • \(^{2}H\): 0.41 x 10^8 rad T^{-1} s^{-1}
  • \(^{13}C\): 0.67 x 10^8 rad T^{-1} s^{-1}
A higher gyromagnetic ratio means a higher Larmor frequency for the same magnetic field strength. Therefore, \(^{1}H\) with a gyromagnetic ratio of 2.7 x 10^8 has a significantly higher Larmor frequency compared to \(^{2}H\) and \(^{13}C\).
Magnetic field strength
In NMR spectroscopy, the strength of the external magnetic field (\(B_0\)) plays a crucial role in determining the Larmor frequency of a nucleus. Fragments in the exercise, we used a magnetic field strength of 4.7 \(T\) to calculate the Larmor frequencies.The relationship between magnetic field strength and Larmor frequency is direct. As you increase the magnetic field strength, the Larmor frequency also increases. This is why high-field NMR spectrometers provide greater resolution and sensitivity.For example, in the exercise, we saw that for a magnetic field strength of 4.7 \(T\):
  • \(^{1}H\) has a Larmor frequency of approximately 202.5 MHz
  • \(^{2}H\) is about 30.7 MHz
  • \(^{13}C\) is around 50.1 MHz
This variation in frequency based on magnetic field strength and type of nucleus is what allows us to distinguish between different substances in NMR spectroscopy.

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Most popular questions from this chapter

The reaction between aqueous \(\mathrm{HCl}\) and 2-pentene gives several products. Two of the products are 3-pentanol and 3-chloropentane. How would you use IR spectroscopy to differentiate between these two products? 2-Pentanol is also formed. Could you distinguish between 3-pentanol and 2-pentanol using IR?

Methoxyethene (methyl vinyl ether) has four signals in its \({ }^{1} \mathrm{H}\) NMR spectrum. The signals are at \(\delta=3.2 \mathrm{ppm}\) \((3 \mathrm{H}), \delta=3.9 \mathrm{ppm}(1 \mathrm{H}), \delta=4.0 \mathrm{ppm}(1 \mathrm{H})\), and \(\delta=6.4 \mathrm{ppm}\) (1H). Assign these signals as accurately as possible and explain your reasoning. Predict the coupling for each signal.

The upfield signal (about \(\delta 0.90 \mathrm{ppm}\) ) in the \({ }^{1} \mathrm{H}\) NMR spectrum of 2-bromo-3-methylbutane is not a \(6 \mathrm{H}\) doublet as we might predict but is actually two \(3 \mathrm{H}\) doublets. Explain.

Compound A was isolated from the bark of the sweet birch (Betula lenta). Chemical test (soluble in \(5 \%\) aqueous \(\mathrm{NaOH}\) solution but not in \(5 \%\) aqueous \(\mathrm{NaHCO}_{3}\) solution) for compound \(\mathbf{A}\) is positive for phenol (p. 233). The spectral data for compound \(\mathbf{A}\) are summarized below. Deduce the structure of compound A. (Be sure to assign the aromatic resonances in the \({ }^{1} \mathrm{H}\) NMR spectrum. Note that long- range coupling was not observed.) Hint: The \(\mathrm{p} K_{\mathrm{a}}\) of phenol is about 10, and that of benzoic acid is about \(4.2 .\) Compound A Mass spectrum: \(m / z=152(\mathrm{M}, 49 \%), 121(29 \%), 120\) (100\%), 92 (54\%) IR (neat): 3205 (br), 1675 (s), 1307 (s), 1253 (s), 1220 (s), and \(757(\mathrm{~s}) \mathrm{cm}^{-1}\) \({ }^{1} \mathrm{H} \mathrm{NMR}\left(\mathrm{CDCl}_{3}, 300 \mathrm{MHz}\right): \delta 3.92(\mathrm{~s}, 3 \mathrm{H})\) $$ \begin{aligned} &6.85(\mathrm{t}, J=8 \mathrm{~Hz}, 1 \mathrm{H}) \\ &7.00(\mathrm{~d}, J=8 \mathrm{~Hz}, 1 \mathrm{H}) \\ &7.44(\mathrm{t}, J=8 \mathrm{~Hz}, 1 \mathrm{H}) \\ &7.83(\mathrm{~d}, J=8 \mathrm{~Hz}, 1 \mathrm{H}) \\ &10.8(\mathrm{~s}, 1 \mathrm{H}) \end{aligned} $$ $$ { }^{13} \mathrm{C} \text { NMR }\left(\mathrm{CDCl}_{3}\right): \delta 52.1 \text { (g), } 112.7 \text { (s), } 117.7 \text { (d), } 119.2 $$ \({ }^{13} \mathrm{C}\) NMR \(\left(\mathrm{CDCl}_{3}\right): \delta 52.1(\mathrm{q}), 112.7(\mathrm{~s}), 117.7(\mathrm{~d}), 119.2\) (d), \(130.1\) (d), \(135.7\) (d), \(162.0\) (s), \(170.7\) (s) (hydrogen coupling indicated in parentheses) Use Organic Reaction Animations (ORA) to answer the following questions:

Isomeric compounds \(\mathbf{A}\) and \(\mathbf{B}\) have the composition \(\mathrm{C}_{11} \mathrm{H}_{12} \mathrm{O}_{4}\). Spectral data are summarized below. Deduce structures for \(\mathbf{A}\) and \(\mathbf{B}\) and explain your reasoning. Compound A IR (KBr): 1720 (s), 1240 (s) \(\mathrm{cm}^{-1}\) \({ }^{1} \mathrm{H} \mathrm{NMR}\left(\mathrm{CDCl}_{3}\right): \delta 2.46(\mathrm{~s}, 3 \mathrm{H})\) $$ \begin{aligned} &3.94(\mathrm{~s}, 6 \mathrm{H}) \\ &8.05(\mathrm{~d}, J=2 \mathrm{~Hz}, 2 \mathrm{H}) \\ &8.49(\mathrm{t}, J=2 \mathrm{~Hz}, 1 \mathrm{H}) \end{aligned} $$ Compound B IR (Nujol): 1720 (s), 1245 (s) \(\mathrm{cm}^{-1}\) \({ }^{1} \mathrm{H} \mathrm{NMR}\left(\mathrm{CDCl}_{3}\right): \delta 2.63(\mathrm{~s}, 3 \mathrm{H})\) $$ \begin{aligned} &3.91(\mathrm{~s}, 6 \mathrm{H}) \\ &7.28(\mathrm{~d}, J=8 \mathrm{~Hz}, 1 \mathrm{H}) \\ &8.00(\mathrm{dd}, J=8 \mathrm{~Hz}, 2 \mathrm{~Hz} ; 1 \mathrm{H}) \\ &\mathrm{dd}=\text { doublet of doublets } \\ &8.52(\mathrm{~d}, J=2 \mathrm{~Hz}, 1 \mathrm{H}) \end{aligned} $$

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