Chapter 13: Problem 14
The area of a \({ }^{1} \mathrm{H}-\mathrm{NMR}\) signal is proportional to the number of equivalent hydrogens giving rise to that signal.
Short Answer
Expert verified
Answer: To determine the number of equivalent hydrogens from a 1H-NMR spectrum, follow these steps: 1) Identify the signal(s) of interest in the spectrum, 2) Measure the area under each identified signal, and 3) Compare these measured areas to determine the relative number of equivalent hydrogens contributing to each signal.
Step by step solution
01
Understanding Equivalent Hydrogens
Equivalent hydrogens are those that experience the same chemical environment in a molecule. This means that they have the same neighboring atoms, bond types, and spatial arrangement. In a 1H-NMR spectrum, these hydrogens produce a single signal with a specific chemical shift, because they all experience the same magnetic environment.
02
1H-NMR Signals and Areas
A 1H-NMR signal is a peak in a spectrum representing the resonance frequency of the hydrogen nucleus in a specific chemical environment. The area under this signal or peak corresponds to the number of equivalent hydrogens that contribute to it.
03
Analyzing 1H-NMR Signals and Areas
To determine the number of equivalent hydrogens from a \({ }^{1} \mathrm{H}-\mathrm{NMR}\) spectrum, consider the following steps:
1. Identify the signal(s) of interest in the spectrum.
2. Measure the area under each identified signal.
3. Compare these measured areas to determine the relative number of equivalent hydrogens contributing to each signal.
04
Example of Analyzing a 1H-NMR Signal
Let's assume we have a \({ }^{1} \mathrm{H}-\mathrm{NMR}\) spectrum with two signals A and B. Signal A has an area of 6 units and Signal B has an area of 2 units.
1. Identify the signals (A and B) in the spectrum.
2. Measure the area under each signal with appropriate NMR analysis software or by estimating the peak areas visually.
3. Compare the measured areas: Signal A (6 units) and Signal B (2 units).
4. Determine the relative number of equivalent hydrogens: There are three times more equivalent hydrogens contributing to Signal A compared to Signal B, because 6 divided by 2 is 3. In this case, we can conclude that there are 6 equivalent hydrogens for Signal A and 2 equivalent hydrogens for Signal B.
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Key Concepts
These are the key concepts you need to understand to accurately answer the question.
Equivalent Hydrogens
When studying 1H-NMR spectroscopy, recognizing equivalent hydrogens is essential. Equivalent hydrogens are atoms of hydrogen within a molecule that occupy identical chemical environments. This means they're connected to the same type of atoms, have similar spatial arrangements, and engage in the same type of bonds. As a result, these hydrogens can't be distinguished from each other by the NMR instrument.
For example, in ethane (C_2H_6), all six hydrogen atoms are equivalent because they're all bonded to carbon atoms, which are in turn bonded to another carbon and three hydrogens. Therefore, in a 1H-NMR spectrum, all six will collectively give rise to one single peak. However, in a molecule like ethanol (CH_3CH_2OH), the hydrogens of the CH_3 group are equivalent to each other but not to the hydrogens in the CH_2 group or the hydroxyl (OH) group due to the different chemical environments.
For example, in ethane (C_2H_6), all six hydrogen atoms are equivalent because they're all bonded to carbon atoms, which are in turn bonded to another carbon and three hydrogens. Therefore, in a 1H-NMR spectrum, all six will collectively give rise to one single peak. However, in a molecule like ethanol (CH_3CH_2OH), the hydrogens of the CH_3 group are equivalent to each other but not to the hydrogens in the CH_2 group or the hydroxyl (OH) group due to the different chemical environments.
Chemical Shift
The chemical shift is a concept in 1H-NMR spectroscopy that represents the resonance frequency of a hydrogen nucleus relative to a reference compound, usually tetramethylsilane (TMS). The shift is a measure of how the electronic environment affects the magnetic field experienced by the hydrogen nuclei.
Different chemical environments result in shifts of the NMR peaks up or downfield. For instance, hydrogen atoms attached to an electronegative atom like oxygen will appear further downfield (higher ppm values) due to the reduced electron density around them, which in turn affects their resonance frequency. A typical chemical shift range for most organic molecules is between 0 to 10 parts per million (ppm). By analyzing these shifts, one can infer a lot about the molecular structure.
Different chemical environments result in shifts of the NMR peaks up or downfield. For instance, hydrogen atoms attached to an electronegative atom like oxygen will appear further downfield (higher ppm values) due to the reduced electron density around them, which in turn affects their resonance frequency. A typical chemical shift range for most organic molecules is between 0 to 10 parts per million (ppm). By analyzing these shifts, one can infer a lot about the molecular structure.
NMR Signal Area
The area under each peak in a 1H-NMR spectrum signifies the ratio of equivalent hydrogens that are contributing to that signal. These areas are integral to quantifying the number of equivalent hydrogens in a molecule.
Modern NMR software is adept at accurately measuring these areas, but understanding the underlying principle is crucial for manual interpretation. For instance, if one peak's area is twice as large as another's, it suggests that there are twice as many equivalent hydrogens contributing to the former peak. The integration of these areas must be compared with each other to determine the precise number of hydrogens responsible for each signal.
Modern NMR software is adept at accurately measuring these areas, but understanding the underlying principle is crucial for manual interpretation. For instance, if one peak's area is twice as large as another's, it suggests that there are twice as many equivalent hydrogens contributing to the former peak. The integration of these areas must be compared with each other to determine the precise number of hydrogens responsible for each signal.
NMR Spectrum Analysis
A 1H-NMR spectrum analysis involves identifying and interpreting various signals to elucidate a compound's structure. This process uses both chemical shifts and signal areas.
Analyzing an NMR spectrum typically involves several steps such as:
Analyzing an NMR spectrum typically involves several steps such as:
- Determining the number of signals, which correlates to distinct chemical environments.
- Measuring and comparing signal areas to find relative numbers of equivalent hydrogens.
- Examining chemical shifts to deduce the electronic environment of the hydrogens.
- Considering splitting patterns, known as spin-spin coupling, which helps in identifying the number and proximity of neighboring hydrogen atoms.