Advanced Organic Chemistry: Mass spectrum of 2-methylbutane (CH3)2CHCH2CH3
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Interpreting and explaining the mass spectrum of 2-methylbutane [Author © Dr Phil Brown GRIC, PhD: Doc Brown's advanced level organic chemistry exam revision notes suitable for students of UK A level chemistry courses & US K12 grade 11, grade 12 and AP honors chemistry courses: Molecular spectrometry - analysing the mass spectrum of 2-methylbutane [spectra page updated RE-EDIT* email doc brown * [privacy, cookies & disclaimer policies] * Re-edit mass spectrum of CH3CH2CH(CH3)2 Links associated with 2-methylbutane This is a BIG chemistry website, please take time to explore it Mass spectrometry - introduction and spectra index See also comparing the infrared, mass, 1H NMR and 13C NMR spectra of the 3 alkane isomers of C5H12 Isomers of molecular formula C5H12 (Mr = 72) Database of accurate m/z values and possible identity of ions formed in mass spectrometry Introductory note on the mass spectrum of 2-methylbutane
2-methylbutane C5H12
For more see The molecular structure and naming of alkanes
[M]+ is the molecular ion peak (M) with an m/z of 72 corresponding to [C5H12]+, the original 2-methylbutane molecule minus an electron, [(CH3)2CHCH2CH3]+ Unless otherwise stated, C means a 12C atom, if not, the isotopic carbon atom 13C will be indicated. The very tiny M+1 peak at m/z 73, corresponds to an ionised 2-methylbutane molecule with one 13C atom in it i.e. an ionised 2-methylbutane molecule of formula [13C12C4H12]+
Identifying the species giving the most prominent peaks (apart from M) in the fragmentation pattern of 2-methylbutane. The most abundant ion of the molecule under mass spectrometry investigation (2-methylbuane) is usually given an arbitrary abundance value of 100, called the base ion peak, and all other abundances ('intensities') are measured against it.
The parent molecular ion is m/z of 72 corresponding to [C5H12]+ or [(CH3)2CHCH2CH3]+
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| m/z | Ion Formula | Fragment Origin | Notes |
|---|---|---|---|
| 72 | C5H12⁺ | Molecular ion (M⁺) | Often weak due to instability |
| 57 | C4H9⁺ | Loss of CH3 (methyl group) | Common in branched alkanes |
| 43 | C3H7⁺ | Loss of C2H5 (ethyl group) or rearrangement | Base peak — very stable ion |
| 41 | C3H5⁺ | Further fragmentation of C3H7⁺ | Less intense, m/z ions 39 and 42 quite prominent |
| 29 | C2H5⁺ | Ethyl cation from deeper fragmentation | Often present |
| 15 | CH3⁺ | Methyl cation | Small peak |
Sources: NIST Mass Spectrometry Database, AQA/Edexcel/OCR specimen papers
Practice
questions based on the mass spectrum of 2-methylbutane
Three varied, technically accurate multiple-choice questions on the mass spectrum of 2-methylbutane (C5H12), suitable for AQA, Edexcel, OCR, WJEC, CCEA, CIE, IB, and US AP/Honors chemistry exams.
These questions explore fragmentation logic, ion stability, and isomer comparison, with model answers and distractor analysis.
In the EI mass spectrum of 2-methylbutane, the base peak appears at m/z 57.
What is the most likely identity and origin of this fragment?
Correct Answer: A
Model Answer:
The molecular ion of 2-methylbutane (M⁺ = 72) fragments by losing a methyl
radical (•CH3),
forming a C4H9⁺
ion (m/z 57). This ion is a secondary carbocation, which is
relatively stable and thus appears as the base peak.
Distractor Analysis:
| Option | Why It’s Incorrect |
|---|---|
| B | C3H3⁺ (m/z 43) is a possible fragment but less stable and less intense than C4H3⁺. |
| C | The molecular ion (m/z 72) is often weak or absent in alkanes due to rapid fragmentation. |
| D | C₂H₅⁺ (m/z 29) is too small and not the dominant fragment in this molecule. |
Which of the following best explains why the mass spectrum of 2-methylbutane differs from that of pentane, even though both have the same molecular formula (C5H12)?
Correct Answer: A
Model Answer:
Both molecules have M⁺ = 72, but
2-methylbutane fragments to form a stable secondary carbocation (C4H9⁺,
m/z 57), while
pentane more commonly fragments to form C3H7⁺
(m/z 43). The difference in
fragment stability and branching leads to distinct base peaks.
Distractor Analysis:
| Option | Why It’s Incorrect |
|---|---|
| B | Neither molecule contains a double bond; both are saturated alkanes. |
| C | Branching affects fragmentation, not the molecular ion mass. |
| D | No halogens are present in either molecule. |
Which of the following best describes the fragmentation mechanism that leads to the m/z 57 peak in the mass spectrum of 2-methylbutane?
Correct Answer: A
Model Answer:
The m/z 57 fragment arises from homolytic cleavage of a
C–C bond, typically adjacent to the branched carbon. This produces a
secondary carbocation (C4H9⁺),
which is stabilized by hyperconjugation and appears as the base peak.
Distractor Analysis:
| Option | Why It’s Incorrect |
|---|---|
| B | Loss of hydrogen would give m/z 71, but this tertiary carbocation is not favoured in this case. |
| C | Cyclic rearrangements are rare in simple alkanes under EI conditions. |
| D | No chlorine is present in 2-methylbutane. |
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Comparing the infrared, mass, 1H NMR and 13C NMR
spectra of the 3 alkane isomers of C5H12 NOTE: The images are linked to their original detailed spectral analysis pages AND can be doubled in size with touch screens to increase the definition to the original pentane, 2-methylbutane and 2,2-dimethylpropane image sizes. |
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Comparing the
infrared
spectra of pentane, 2-methylbutane and 2,2-dimethylpropane Pentane, 2-methylbutane and 2,2-dimethylpropane are structural isomers of molecular formula C5H12 Pentane, 2-methylbutane and 2,2-dimethylpropane exemplify infrared spectra of the alkane homologous series CnH2n+2 hydrocarbon molecules, where n = 5 |
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INFRARED SPECTRA (above): There are, as expected, differences in the fingerprint region at wavenumbers 1500 to 400 cm-1, but there is no specific infrared absorption band for a functional group. The infrared spectra of pentane and 2-methylbutane seem very similar, but that of 2,2-dimethylpropane seems much simpler. |
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Comparing the
mass
spectra of pentane, 2-methylbutane and 2,2-dimethylpropane Pentane, 2-methylbutane and 2,2-dimethylpropane are structural isomers of molecular formula C5H12 Pentane, 2-methylbutane and 2,2-dimethylpropane exemplify the mass spectra of the alkane series CnH2n+2 hydrocarbon molecules, where n = 5 |
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MASS SPECTRA (above): All three hydrocarbons show some similarities in their mass spectra e.g. m/z ions 27 to 29 for [C2Hx]+ (x = 2 and 4). The molecular ion peaks will be the same for all three isomers (m/z 72), but it is very tiny for 2,2-dimethypropane. The pattern ratios for m/z 39 to 43 are similar for pentane and 2-methylbutane, but m/z 42 and 43 ions are almost absent from the 2,2-dimethylpropane spectrum. The base peak ion for pentane is m/z 43, but for 2-methylbutane and 2,2-dimethylpropane it is m/z 57. |
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Comparing the
1H proton NMR
spectra of pentane, 2-methylbutane and 2,2-dimethylpropane Pentane, 2-methylbutane and 2,2-dimethylpropane are structural isomers of molecular formula C5H12 Pentane, 2-methylbutane and 2,2-dimethylpropane exemplify the 1H proton NMR spectra of the alkane homologous series CnH2n+2 hydrocarbon molecules where, n = 5 |
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1H NMR SPECTRA (above): The 1H NMR spectra of all three molecules give different proton ratios for the different 1H chemical environments i.e. pentane's proton ratio is 3:2:1 (from 6:4:2 H's in the molecule). 2-methylbutane's proton ratio is 6:1:2:3 and 2,2-dimethylpropane's doesn't have a proton ratio, all hydrogen atoms are equivalent. This means all three isomeric C5H12 hydrocarbons can be distinguished from their 1H NMR spectra. |
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Comparing the
carbon-13 NMR
spectra of pentane, 2-methylbutane and 2,2-dimethylpropane Pentane, 2-methylbutane and 2,2-dimethylpropane are structural isomers of molecular formula C5H12 Pentane, 2-methylbutane and 2,2-dimethylpropane exemplify the carbon-13 NMR spectra of members of the alkane homologous series CnH2n+2 hydrocarbon molecules, where n = 5 |
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13C NMR SPECTRA (above): The 13C NMR spectra of the three molecules show different numbers of carbon-13 chemical environments i.e different numbers of 13C NMR resonance lines. So, pentane gives three 13C chemical shifts, 2-methylbutane four and 2,2-dimethylpropane two. This means all three isomeric C5H12 hydrocarbons can be distinguished from their 13C NMR spectra. |
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Key words & phrases: isopentane methylbutane image diagram on how to interpret and explain the mass spectrum of 2-methylbutane m/z m/e base peaks, image and diagram of the mass spectrum of 2-methylbutane, details of the mass spectroscopy of 2-methylbutane, low and high resolution mass spectrum of 2-methylbutane, prominent m/z peaks in the mass spectrum of 2-methylbutane, comparative mass spectra of 2-methylbutane, the molecular ion peak in the mass spectrum of 2-methylbutane, analysing and understanding the fragmentation pattern of the mass spectrum of 2-methylbutane, characteristic pattern of peaks in the mass spectrum of 2-methylbutane, relative abundance of mass ion peaks in the mass spectrum of 2-methylbutane, revising the mass spectrum of 2-methylbutane, revision of mass spectroscopy of 2-methylbutane, most abundant ions in the mass spectrum of 2-methylbutane, how to construct the mass spectrum diagram for abundance of fragmentation ions in the mass spectrum of 2-methylbutane, how to analyse the mass spectrum of 2-methylbutane, how to describe explain the formation of fragmented ions in the mass spectra of 2-methylbutane equations for explaining the formation of the positive ions in the fragmentation of the ionised molecule of 2-methylbutane recognising the base ion peak of 2-methylbutane isopentane methylbutane Stick diagram of the relative abundance of ionised fragments in the fingerprint pattern of the mass spectrum of 2-methylbutane. Table of the m/e m/z values and formula of the ionised fragments in the mass spectrum of 2-methylbutane. The m/e m/z value of the molecular ion peak in the mass spectrum of 2-methylbutane. The m/e m/z value of the base ion peak in the mass spectrum of 2-methylbutane. Possible examples of equations showing the formation of the ionised fragments in 2-methylbutane. Revision notes on the mass spectrum of 2-methylbutane. Matching and deducing the structure of the 2-methylbutane molecule from its mass spectrum. Mass spectroscopy of aliphatic alkanes, mass spectra of 2-methylbutane, an isomer of molecular formula C5H12
How do you interpret the mass spectrum of 2-methylbutane How to interpret the mass spectrum of 2-methylbutane Explanatory diagram of the mass spectrum of the 2-methylbutane molecule in terms of its molecular structure. Listing data of the prominent main peaks in the mass spectrum of 2-methylbutane. How to explain the mass spectrum of 2-methylbutane. The m/z value of the molecular ion peak in the mass spectrum of 2-methylbutane. Identifying 2-methylbutane from its mass spectrum pattern. The m/z m/e peak analysis of the mass spectrum of the 2-methylbutane molecule. The uses of the mass spectrum of the 2-methylbutane molecule. The distinctive features of the mass spectrum of the 2-methylbutane molecule explained. explaining the fragmentation pattern of the mass spectrum of 2-methylbutane equations showing the formation of the ionised fragments in the mass spectrum of 2-methylbutane what does the mass spectrum tell you about the structure and properties of the 2-methylbutane molecule? Data table of ionised fragments in the mass spectrum of 2-methylbutane and equations for their formation in the fragmentation of 2-methylbutane moleculesLinks associated with 2-methylbutane
The infrared spectrum for 2-methylbutane
The H-1 NMR spectrum for 2-methylbutane
The C-13 NMR spectrum for 2-methylbutane
Mass spectrometry - introduction and spectra index
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